Catalyst system for the polymerization of alkenes to polyolefins

ABSTRACT

The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M W )in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

RELATED APPLICATION DATA

[0001] This patent application is a divisional of and claims priority ofU.S. application Ser. No. 09/488,431 filed Jan. 20, 2000, now allowed,which claims the benefit of provisional applications Serial No.60/116,522 filed Jan. 20, 1999, Serial No. 60/116,646 filed Jan. 20,1999 and Serial No. 60/150,083 filed Aug. 20, 1999, the entiredisclosures of which are herein incorporated by reference.

GOVERNMENT SUPPORT

[0002] The government may have certain rights in this invention pursuantto Grant No. DE-FG03-88ER13431 from the Department of Energy.

FIELD OF THE INVENTION

[0003] This invention relates to catalysts, catalyst systems and methodsof production of olefin polymers, including isotactic, syndiotactic andstereoblock polymer, and the polymers produced thereby.

BACKGROUND

[0004] The mechanical properties of a given polymer can generally beclassified as rigid, flexible, or elastic. While metallocene catalystsare capable of producing polymers that fall into each of theseclassifications, the most intense efforts have been directed atsurpassing existing systems in their aptitude for making rigid isotacticpolypropylene and rigid or flexible polyethylene [1] More recently,growing efforts to devise metallocene catalysts capable of producingelastomeric polymers have revealed several different viable strategies:ethylene/α-olefin copolymers [2]; high molecular weight atacticpolypropylene [3]; binary isotactic/atactic compatibilized polypropylene[4]; isotactic-atactic polypropylene [5]; stereoblock isotactic-atacticpolypropylene [6]; and isotactic polypropylene with controllablestereoerror sequences. [7] Although the structure/property relationshipof each of these regimes is not fully understood, the elastomericproperties undoubtedly rely on the existence of physical crosslinks inthe presence of an amorphous phase. In the case of high molecular weightmaterials, the crosslinks can be simple chain entanglements. In theother examples, segments from several different polymer chainsparticipate in crystalline regions, which physically connect the chainsand provide crosslinks in an otherwise amorphous phase.

[0005] One of the best understood systems is that initially developed byCoates and Waymouth. [6, 8] Their unbridged metallocene(2-phenylindenyl)₂ZrCl₂, in the presence of methylaluminoxane (MAO),isomerizes between chiral and achiral coordination geometries during theformation of a given polypropylene chain. Since the chiral isomer isisospecific and the achiral isomer is aspecific, stereoblockisotactic-atactic polypropylene is obtained.

[0006] Elastomeric and other polyolefins with controlledstereostructures are useful for a wide variety of applications. Novelpolyolefins, especially those with elastomeric properties, can be usefulfor a wide variety of applications. Accordingly, there is a need forcatalyst systems capable of polymerizing alkenes to novel polyolefins.

[0007] There is also a need to develop catalysts sufficiently stable tobe used on an industrial scale. Owing to the chelate effect, bridgedmetallocene catalysts tend to be more stable at elevated polymerizationtemperatures, and often behave more predictably when adsorbed on asupport, a common industrial tactic.

[0008] Accordingly, there is a need for stable, readily synthesizedcatalyst systems capable of controlled polymerization of alkenes to givepolyolefins.

SUMMARY

[0009] The invention provides bridged metallocene catalyst systems thatare useful for the controlled polymerization of alkenes to polyolefins.Also provided are catalyst systems useful for polymerizing a variety ofalkene monomers into stereocontrolled polymers including isotacticpolymers, syndiotactic polymers and stereoblock polymers containing bothhemiisotactic and isotactic regions. Catalysts of the invention can bechosen to provide a specific size range of produced polymers. Catalystsalso can be chosen so as to produce a polymer with a desiredmicrostructure.

[0010] This invention describes a new catalyst system for polymerizingC₂ to C₁₀ alk-1-enes to produce polyolefin polymers. The catalyst systemincludes two components: (a) an organometallic compound of the generalformula (II),

[0011] in which M is a metal of the III, IV, or V subgroup of theperiodic system or a metal from the lanthamide or actinide groups; X isfluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀ alkyl, C₆ toC₂₀ aryl, alkylaryl, arylalkyl, fluoroalkyl, or fluoroaryl having 1 to10 20 carbons in the alkyl moiety and 6 to 20 carbon atoms in the arylmoiety, or —OR¹⁷ where R¹⁷ is a C₁ to C₁₀ alkyl or C₆ to C₂₀ aryl; n isthe formal oxidation state of M minus 2; E¹ is hydrogen, carbon,silicon, or germanium; E² is carbon, silicon, or germanium; R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are,independently, hydrogen, C₁ to C₁₀ alkyl, 3 to 10 membered cycloalkyl,which in turn may have from 1 to 10 C₁ to C₁₀ alkyls as substituents, C₆to C₁₆ aryl or arylalkyl in which two adjacent substituents may togetherstand for cyclic groups having 4 to 16 carbon atoms which in turn may besubstituted, or Si(R¹⁸)₃ where R¹⁸ is a C₁ to C₁₀ alkyl, C₆ to C₁₆ arylor C₃ to C₁₀ cycloalkyl; and where E¹ is hydrogen, R¹, R² and R³ areabsent; or an organometallic compound of the general formula (III),

[0012] in which M is a metal of the III, IV, or V subgroup of theperiodic system or a metal from the lanthamide or actinide groups; X isfluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀ alkyl, C₆ toC₂₀ aryl, alkylaryl, arylalkyl, fluoroalkyl, or fluoroaryl having 1 to10 carbons in the alkyl moiety and 6 to 20 carbon atoms in the arylmoiety, or —OR¹³ where R¹³ is a C₁ to C₁₀ alkyl or C₆ to C₂₀aryl; n isthe formal oxidation state of M minus 2; E¹ is hydrogen, carbon,silicon, or germanium; E² is carbon, silicon, or germanium; R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R¹² are, independently, hydrogen,C₁ to C₁₀alkyl, 3 to 10 membered cycloalkyl, which in turn may have from1 to 10 C₁ to C₁₀ alkyls as substituents, C₆ to C₁₆ aryl or arylalkyl inwhich two adjacent substituents may together stand for cyclic groupshaving 4 to 16 carbon atoms which in turn may be substituted, orSi(R¹⁴)₃ where R¹⁴ is a C₁ to C₁₀ alkyl, C₆ to C₁₆ aryl or C₃ to C₁₀cycloalkyl; and where E¹ is hydrogen, R¹, R² and R³ are absent; and (b)an activator.

[0013] Catalyst System for Isotactic Polyolefins

[0014] Metallocene catalysts can be chosen according to the inventionthat produce isotactic polyolefins. The preferred catalyst forpolymerizing C₂ to C₁₀ alk-1-enes to produce isotactic polyolefins iscompound II or compound III wherein no elements of symmetry exist; thatis, compound II or compound III are of C, symmetry. It is generallypreferred that the R¹, R², R³, and E¹ group is a sterically large group,for example an adamantyl group. The preferred metals are titanium,zirconium, hafnium, scandium, and yttrium. The preferred X are chlorine,bromine, hydrogen, methyl, phenyl, and benzyl. The preferred E² iscarbon or silicon. The preferred R substituents are as follows: For II,R¹, R², R³, and E¹ constitute the 2-methyl-2-adamantyl group; R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are hydrogen; R¹⁵ and R¹⁶are methyl, phenyl, or part of a cycloalkyl group, including cyclohexylor adamantyl. For III, R¹, R², R³, and E¹ constitute the2-methyl-2-adamantyl group; R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ arehydrogen; R¹¹ and R¹² are methyl, phenyl, or part of a cycloalkyl group,including cyclohexyl or adamantyl.

[0015] Catalyst System for Syndiotactic Polyolefins

[0016] Catalyst systems also can be prepared that preferentiallycatalyze the formation of syndiotactic polyolefins from alkeneprecursors. The preferred catalyst for polymerizing C₂ to C₁₀ alk-1-enesto produce syndiotactic polyolefins is compound III wherein a mirrorplane of symmetry exists; that is, compound III is of C_(s) symmetry.The preferred metals are titanium, zirconium, hafiium, scandium, andyttrium. The preferred X are chlorine, bromine, hydrogen, methyl,phenyl, and benzyl. The preferred E¹ is carbon or silicon. The preferredR substituents are as follows: E¹ is hydrogen, R¹, R² and R³ are absent;R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ and R¹⁰ are hydrogen; R¹¹ and R¹² are methyl,phenyl, or part of a cycloalkyl group, including cyclohexyl oradamantyl.

[0017] Catalyst System for Elastomeric Polyolefins

[0018] The preferred catalyst for polymerizing C₂ to C₁₀ alk-1-enes toproduce stereoblock isotactic-hemiisotactic polyolefins is compound IIwherein there are no symmetry elements; that is, compound II is of C₁symmetry. The preferred metals are titanium, zirconium, hafnium,scandium, and yttrium. The preferred X are chlorine, bromine, hydrogen,methyl, phenyl, and benzyl. The preferred E¹ and E² are carbon andsilicon. The preferred R substituents are as follows: R¹ is hydrogen;R², and R³ are, independently, hydrogen, methyl, ethyl, isopropyl,tert-butyl, phenyl, trimethylsilyl, or part of a cycloalkyl group,including cyclohexyl, adamantyl, or 3,3,5,5-tetramethylcyclohexyl; R⁴,R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴ are hydrogen or methyl;and R¹⁵ and R¹⁶ are hydrogen, methyl, or phenyl.

[0019] Polyolefin Polymerization

[0020] The metallocenes of the present invention, in the presence ofappropriate activators, are useful for the polymerization of alkenes,including ethylene and alpha-olefins, for example propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene and combinations thereof. Thepolymerization of olefins is carried out by contacting the olefin withthe catalyst systems comprising the transition metal component and inthe presence of an appropriate cocatalyst, for example an alumoxane, ora Lewis acid for example B(C₆F₅)₃, or a protic acid containing anon-coordinating anion, for example [PhNMe₂H]⁺B(C₆F₅)₄ ⁻. Conditionssuitable for the polymerization of olefins to polyolefins are known inthe art. Suitable temperatures, pressures, and optional solvents can bedetermined by one of skill in the art for use in the present invention.

[0021] The metallocene catalyst systems of the present invention areuseful for the polymerization of alkenes to polyolefins. In particular,catalysts can be selected to produce isotactic or syndiotacticpolypropylene. Examples of catalysts suitable for the production of aparticular type of catalyst are given above and in the followingExamples. In one embodiment, the alkenes to be polymerized are alphaolefins.

[0022] The metallocene catalyst systems of the present invention areparticularly useful for the polymerization of propylene to producepolypropylenes with novel elastomeric properties. By elastomeric, wemean a material which tends to regain its shape upon extension, or onewhich exhibits a positive power of recovery at 100%, 200% and 300%elongation. The properties of elastomers are characterized by severalvariables. The initial modulus is the resistance to elongation at theonset of stretching. This quantity is simply the slope at the beginningof the stress-strain curve. Upon overstretching, the polymer sampleeventually ruptures. The rupture point yields two importantmeasurements, the tensile strength (T_(b)) and the ultimate elongation(E_(b)). These values are the stress and percent elongation at thebreak, respectively. The tensile set (TS) is the elongation remaining ina polymer sample after it is stretched to 300% elongation and allowed torecover. An additional measure of the reversibility of stretching is thepercent recovery (PR), which is given by the equation: 100(finallength−initial length)/(initial length).

[0023] It is believed that the elastomeric properties of thepolypropylenes of this invention are due to an alternating blockstructure comprising of isotactic and hemiisotactic stereosequences.Without being bound by theory, it is believed that isotactic blockstereosequences provide crystalline blocks which can act as physicalcrosslinks in the polymer network.

[0024] The structure of the polymer can be described in terms of theisotactic pentad content [mmmm] which is the percentage of isotacticstereosequences of 5 contiguous stereocenters, as determined by ¹³C NMRspectroscopy (Zambelli, A. et al. 1975. Macromolecules 8, 687-689). Theisotactic pentad content of statistically atactic polypropylene isapproximately 6.25%, while that of highly isotactic polypropylene canapproach 100%. Polymers also can be characterized for their isotacticpercent (m).

[0025] While it is possible to produce polypropylenes with a range ofisotactic pentad contents, the elastomeric properties of the polymerwill depend on the distribution of isotactic (crystalline) and atactic(amorphous) stereosequences. Thermoplastic elastomers consist ofamorphous-crystalline block polymers, and thus the blockiness of thepolymer determines whether it will be elastomeric.

[0026] The structure, and therefore the properties of the obtainedpolypropylenes also depend on the nature of the ligand bound to thetransition metal.

[0027] It will be appreciated from the illustrative examples that thiscatalyst system provides an extraordinary broad range of polymerproperties from the polymerization process of this invention.

[0028] Polyolefins can be obtained by suitable manipulation of themetallocene catalyst, the reaction conditions, or the cocatalyst to givepolymers which range in properties from gum elastomers to thermoplasticelastomers to flexible thermoplastics, and indeed, to relatively rigidthermoplastics.

[0029] The polymers of the present invention in one embodiment are anovel class of thermoplastic elastomers made up of propylenehomopolymers of weight average molecular weights ranging from 20,000 toabove about 2 million. Preferably, the average molecular weights of thepolypropylenes are very high, as molecular weights on the average of1,000,000 are readily obtainable and even higher M_(w) are indicated.The molecular weight distributions of the polymers are quite low, withtypical polydispersities, M_(w)/M_(n), ranging from about 1.8 to about4.4, and more preferably can be controlled to be in the range of about1.8 to about 2.4. However, by control of reaction conditions, highermolecular weight distributions also can be obtained, e.g.,polydispersities of 5-20 are easily produced. The elastomericpolypropylenes of the present invention have isotactic pentad contentsranging from an [mmmm] content of about 25% to an [mmmm] of about 50%.The polypropylenes of the present invention range from amorphous atacticpolypropylenes with no melting point, to elastomeric polypropylenes ofhigh crystallinity with melting points up to about 160° C.

[0030] Accordingly, because of the wide range of structures andcrystallinities, the polypropylenes of the present invention exhibit arange of properties from gum elastomers, to thermoplastic elastomers, toflexible thermoplastics. The range of elastomeric properties for thepolypropylenes is quite broad. Properties of particular polymers of theinvention are listed in the Tables.

[0031] The polypropylenes of the present invention can be melt spun intofibers, or can be cast into transparent, tough, self-supporting filmswith good elastic recoveries. Thin films of elastomeric polypropyleneswith isotactic pentad contents [mmmm]=30% are slightly opaque, butexhibit stress-whitening upon extension, which may be indicative ofstress-induced crystallization. The elastomeric polypropylenes can alsobe cast into molded articles.

[0032] The elastomeric polypropylenes of the present invention can beblended with isotactic polypropylenes, including isotacticpolypropylenes of the invention. The melting points and heats of fusionof the blends increase steadily with increasing mole fraction ofisotactic polypropylene in the blend.

[0033] The utility of the polymers of the present invention are evidentand quite broad, including films, adhesives, resilient and elastomericobjects. As they are completely compatible with isotactic polypropylene,they are ideal candidate additives to improve the toughness and impactstrength of isotactic polypropylenes.

[0034] Isotactic Polyolefins

[0035] This invention describes a new material synthesized from C₂ toC₁₀ alk-1-enes by a catalyst system. The polymer formed is athermoplastic [1] and has the general microstructure and tacticitydepicted by formula (IV):

[0036] in which R1 is C₁ to C₈ alkyl, 3 to 10 membered cycloalkyl, C₆ toC₂₀ aryl, alkylaryl, arylalkyl, fluoroalkyl, or fluoroaryl having 1 to10 carbons in the alkyl moiety and 6 to 20 carbon atoms in the arylmoiety, Si(R⁴)₃ where R⁴ is a C₁ to C₁₀ alkyl, or —OR⁵ where R⁵ ishydrogen, C₁ to C₁₀ alkyl or C₆ to C₂₀ aryl; R² and R³ are independentlyhydrogen, C₁ to C₁₀ alkyl, C₂ to C₁₀ alkenyl, or OR⁵; n is greater than0.

[0037] The preferred isotactic polymer structure is polyolefin IVwherein R¹ is methyl, R² is hydrogen, ethenyl, isopropyl, orisopropenyl, and R³ is hydrogen or methyl. The preferred n is greaterthan 0. The preferred polymer tacticity is thus isotactic. The preferredthermo-mechanical properties of the polymer are those of athermoplastic.

[0038] This new polymer may be prepared via monomer polymerizationprocesses that occur homogeneously in solution, supported in a solution,in the gas phase, at high pressure, or in bulk monomer, including thecondensed phase of lower molecular weight alk-1-enes. The preferredprocesses are bulk monomer and gas phase polymerization methods.Catalyst systems may be organometallic compounds containing a metal ofthe III, IV, or V subgroup of the periodic system, or a metal from thelanthamide or actinide groups, activated by systems which may bealkylaluminums, haloalkylaluminums, alkylaluminoxanes or ionicactivators. The preferred organometallic precatalysts are(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl) (fluorenyl)zirconium dichloride (71, “R₂C(Cp¹)(Flu¹)zirconium dichloride”) and(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl) zirconium dichloride (72,“R₂C(Cp²)(Oct¹)zirconium dichloride”). The preferred activators aremethylaluminoxane and activators which contain boron.

[0039] Most preferably, the produced polyolefin will be a high meltingthermoplastic. Polymerization of two or more monomers may be employed toproduce copolymers or terpolymers. Combinations of two or moremetallocene catalyst precursors may be used to prepare a blend ofpolymers. The polymers, copolymers, and terpolymers prepared accordingto this invention may be blended with existing, commercial polyolefins.

[0040] Isotactic polymers produced with the catalysts of the inventionhave catalytic dyad (mm) contents of at least about 98% and can have mmcontent of >99%. Catalysts of the invention are particularly suited tothe production of isotactic polypropylene.

[0041] Syndiotactic Polyolefins

[0042] This invention also describes a new material synthesized from C₂to C₁₀ alk-1-enes by a catalyst system. The polymer formed is athermoplastic^(1,2) and has the general microstructure and tacticitydepicted by formula (I)

[0043] in which R¹ is C₁ to C₈ alkyl, 3 to 10 membered cycloalkyl, C₆ toC₂₀ aryl, alkylaryl, arylalkyl, fluoroalkyl, or fluoroaryl having 1 to10 carbons in the alkyl moiety and 6 to 20 carbon atoms in the arylmoiety, Si(R⁴)₃ where R⁴ is a C₁ to C₁₀ alkyl, or —OR⁵ where R⁵ ishydrogen, C₁ to C₁₀ alkyl or C₆ to C₂₀ aryl; R² and R³ are independentlyhydrogen, C₁ to C₁₀ alkyl, C₂ to C₁₀ alkenyl, or oR⁵; n is greater than0.

[0044] The preferred polymer structure is polyolefin V wherein R¹ ismethyl, R² is hydrogen, ethenyl, isopropyl, or isopropenyl, and R³ ishydrogen or methyl. The preferred n is greater than 0. The preferredpolymer tacticity is thus syndiotactic. The preferred thermo-mechanicalproperties of the polymer are those of a thermoplastic.

[0045] Method of Preparing Syndiotactic Polyolefins

[0046] This new polymer may be polymerized via monomer polymerizationprocesses that occur homogeneously in solution, supported in a solution,in the gas phase, at high pressure, or in bulk monomer, including thecondensed phase of lower molecular weight alk-1-enes. The preferredprocesses are bulk monomer and gas phase polymerization methods.Catalyst systems may be organometallic compounds containing a metal ofthe III, IV, or V subgroup of the periodic system, or a metal from thelanthamide or actinide groups, activated by systems which may bealkylaluminums, haloalkylaluminums, alkylaluminoxanes or ionicactivators. The preferred organometallic precatalysts are(methyl)₂C(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (91) and(phenyl)₂C(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride (92). The preferred activators are methylaluminoxane andactivators which contain boron.

[0047] Most preferably, the produced polyolefin will be a high meltingthermoplastic. Polymerization of two or more monomers may be employed toproduce copolymers or terpolymers. Combinations of two or moremetallocene catalyst precursors may be used to prepare a blend ofpolymers. The polymers, copolymers, and terpolymers prepared accordingto this invention may be blended with existing, commercial polyolefins.

[0048] Elastomeric Polyolefins

[0049] This invention describes a new material synthesized from C₂ toC₁₀ alk-1-enes by a catalyst system. The polymer formed is athermoplastic elastomer¹ and has the general microstructure andtacticity depicted by formula (Z)

[0050] in which R¹ is C₁ to C₈ alkyl, 3 to 10 membered cycloalkyl, C₆ toC₂₀ aryl, alkylaryl, arylalkyl, fluoroalkyl, or fluoroaryl having 1 to10 carbons in the alkyl moiety and 6 to 20 carbon atoms in the arylmoiety, Si(R⁴)₃ where R⁴ is a C₁ to C₁₀ alkyl, or —OR⁵ where R⁵ ishydrogen, C₁ to C₁₀ alkyl or C₆ to C₂₀ aryl; R² and R³ are independentlyhydrogen, C₁ to C₁₀ alkyl, C₂ to C₁₀ alkenyl, or OR⁵; m, n, and p areeach greater than 0.

[0051] The preferred elastomeric polymer structure is polyolefin VIwherein R¹ is methyl, R² is hydrogen, ethenyl, isopropyl, orisopropenyl, and R³ is hydrogen or methyl. The preferred m is greaterthan 5 but less than 50% of the degree of polymerization, which is givenby (P)·(m_(average)+2n_(average)). The preferred n is greater than 5 butless than 25% of the degree of polymerization. The preferred p isgreater than 0. The preferred polymer tacticity is thus stereoblockisotactic-hemiisotactic. The preferred therno-mechanical properties ofthe polymer are those of a thermoplastic elastomer.

[0052] This new polymer may be polymerized via monomer polymerizationprocesses that occur homogeneously in solution, supported in a solution,in the gas phase, at high pressure, or in bulk monomer, including thecondensed phase of lower molecular weight alk-1-enes. The preferredprocesses are bulk monomer and gas phase polymerization methods.Catalyst systems may be organometallic compounds containing a metal ofthe III, IV, or V subgroup of the periodic system, or a metal from thelanthamide or actinide groups, activated by systems which may bealkylaluminums, haloalkylaluminums, alkylaluminoxanes or ionicactivators. The preferred organometallic precatalysts are(methyl)₂C(3-(2-adamantyl)cyclopentadienyl) (fluorenyl)zirconiumdichloride (91) and (phenyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (92). The preferred activators aremethylaluminoxane and activators which contain boron.

[0053] Most preferably, the produced polyolefin will be a thermoplasticelastomer containing alternating isotactic and hemiisotacticstereoblocks. Polymerization of two or more monomers may be employed toproduce copolymers or terpolymers. Combinations of two or moremetaliocene catalyst precursors may be used to prepare a blend ofpolymers. The polymers, copolymers, and terpolymers prepared accordingto this invention may be blended with existing, commercial polyolefins.

[0054] Activators

[0055] Appropriate activators for use with the metallocene catalysts ofthe invention include alkylaluminum compounds, methylaluminoxane, ormodified methylaluminoxanes of the type described in the followingreferences: U.S. Pat. No. 4,542,199 to Kaminsky, et al; Ewen, J. Am.Chem. Soc., 106 (1984), p. 6355; Ewen, et al., J. Am. Chem. Soc. 109(1987) p. 6544; Ewen, et al, J. Am. Chem. Soc. 110 (1988), p. 6255.;Kaminsky, et al., Angew. Chem., Int. Ed. Eng. 24 (1985), p. 507. Othercocatalysts which may be used include Lewis or protic acids, whichgenerate cationic metallocenes with compatible non-coordinating anionsfor example B(C₆F₅)₃ or [PhNMe₂H]⁺B(C₆F₅)⁻ ₄ in the presence or absenceof alkylaluminum compounds. Catalyst systems employing a cationic Group4 metallocene and compatible non-coordinating anions are described inEuropean Patent Applications 277,003 and 277,004 filed on 27.01.88 byTurner, et al.; European Patent Application 427,697-A2 filed on 09.10.90by Ewen, et al.; Marks, et al., J. Am. Chem. Soc., 113 (1991), p. 3623;Chien et al., J. Am. Chem. Soc., 113 (1991), p. 8570; Bochman et al.,Angew. Chem. Intl. Ed. Engl. 7 (1990), p. 780; and Teuben et al.,Organometallics, 11 (1992), P. 362, and references therein.

[0056] Utility

[0057] As thermoplastics, these new materials may be processed viamethods including injection molding, extrusion, or blow molding and mayhave applications that take advantage of its mechanical behavior andmechanical properties, including its tensile strength, rigidity andimpact strength. Additional properties of this material may includerecyclability, chemical resistivity, thermal stability, electricalconductivity, optical transparency, and processability.

DETAILED DESCRIPTION

[0058] Definitions

[0059] The term “alkyl” as used herein refers to a branched orunbranched saturated hydrocarbon group of 1 to 24 carbon atoms, forexample methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl,octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like,as well as cycloalkyl groups for example cyclopentyl, cyclohexyl and thelike. The term “lower alkyl” intends an alkyl group of 1 to 6 carbonatoms, preferably 1 to 4 carbon atoms. Alkyl substituents includesoptionally substituted.

[0060] The term “cycloalkyl” as used herein refers to a cyclichydrocarbon of 4 to 10 carbon atoms forming a ring, including bicyclicsystems.

[0061] The term “substituted cycloalkyl” as used herein refers to acycloalkyl ring having substituents on said ring of alkyl, alkoxy,“Substituted cycloalkyl” includes substitution with from 1 to 10 carbonsat each ring position, with a total number of carbon substitutions inthe range of 1 to 30.

[0062] A “cyclic group” is a ring composed of 4 to 10 atoms selectedfrom carbon, silicon, oxygen, sulfur, selenium, and germanium.

[0063] The term “alkoxy” as used herein intends an alkyl group boundthrough a single, terminal ether linkage; that is, an “alkoxy” group maybe defined as —OR where R is alkyl as defined above. A “lower alkoxy”group intends an alkoxy group containing one to six, more preferably oneto four, carbon atoms.

[0064] The term “aryl” as used herein refers to an aromatic speciescontaining 1 to 5 aromatic rings, either fused or linked, and eitherunsubstituted or substituted with 1 or more substituents typicallyselected from the group consisting of —(CH₂)_(x)—NH₂, —(CH₂)_(x)—COOH,—NO₂, halogen and lower alkyl, where x is an integer in the range of 0to 6 inclusive as outlined above. Preferred aryl substituents contain 1to 3 fused aromatic rings, and particularly preferred aryl substituentscontain 1 aromatic ring or 2 fused aromatic rings. The term “aralkyl”intends a moiety containing both alkyl and aryl species, typicallycontaining less than about 24 carbon atoms, and more typically less thanabout 12 carbon atoms in the alkyl segment of the moiety, and typicallycontaining 1 to 5 aromatic rings. The term “aralkyl” will usually beused to refer to aryl-substituted alkyl groups. The term “aralkylene”will be used in a similar manner to refer to moieties containing bothalkylene and aryl species, typically containing less than about 24carbon atoms in the alkylene portion and 1 to 5 aromatic rings in thearyl portion, and typically aryl-substituted alkylene. Exemplary aralkylgroups have the structure —(CH₂)_(j)—Ar wherein j is an integer in therange of 1 to 24, more typically 1 to 6, and Ar is a monocyclic arylmoiety.

[0065] “Halo” or “halogen” refers to fluoro, chloro, bromo or iodo, andusually relates to halo substitution for a hydrogen atom in an organiccompound. Of the halos, chloro and fluoro are generally preferred.

[0066] “Hydrocarbyl” refers to unsubstituted and substituted hydrocarbylradicals containing 1 to about 20 carbon atoms, including branched orunbranched, saturated or unsaturated species, for example alkyl groups,alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl”intends a hydrocarbyl group of one to six carbon atoms, preferably oneto four carbon atoms.

[0067] “Optional” or “optionally” means that the subsequently describedevent or circumstance may or may not occur, and that the descriptionincludes instances where said event or circumstance occurs and instanceswhere it does not. For example, the phrase “optionally substitutedalkyl” means that an alkyl moiety may or may not be substituted and thatthe description includes both unsubstituted alkylene and alkylene wherethere is substitution.

[0068] Substitution of an alkyl, aryl or other hydrocarbon means that ahydrogen of the hydrocarbon is substituted with another atom or group ofatoms. Such atoms include halogens. Groups of atoms can by alkylsubstituents, aryl substituents, aralkyl, alkoxy and the likesubstituents.

[0069] Methods of Preparing Catalysts

[0070] Metallocenes Containing the Fluorene Ligand

[0071] Substituted fulvene [Fulvene¹] can be prepared by known methods.The anion [Flu¹]⁻ is prepared by treatment of [Flu¹]H with alkalimetal-alkyls or Grignard reagents in a solvent to give the correspondingsubstituted fluorenyl anion.

[0072] In a solvent, R¹⁵R¹⁶E²(Flu¹H)(Cp¹H) is formed by combining[Fulvenel] and [Flu¹]⁻, followed by quenching with a proton source, forexample water.

[0073] The dianion of R¹⁵R¹⁶E²(Flu¹H)(Cp¹H) is formed by treatment withalkali metal-alkyls or Grignard reagents in a solvent:[R¹⁵R¹⁶E²(Flu¹)(Cp¹)]⁻². Reaction of this dianion with MX_(n+2) in asolvent produces compound (II), which is isolated according to knownmethods.

[0074] Metallocenes Containing the OctamethyloctahydrodibenzofluoreneLigand

[0075] 1,1,4,4,7,7,10,10-octamethyl-1,2,3,4,7,8,9,10-octahydrodibenzo[b, h] fluorene (OctH) is prepared by the reaction of twoequivalents of 2,5-dichloro-2,5-dimethylhexane with one equivalent offluorene in a solvent in the presence of a Friedel-Crafts initiator.

[0076] Substituted fulvene [Fulvene 2] can be prepared by known methods.The anion [Oct¹]⁻ is prepared by treatment of [Oct¹]H with alkalimetal-alkyls or Grignard reagents in a solvent to give the correspondingsubstituted octamethyloctahydrodibenzofluorenyl anion.

[0077] In a solvent, R¹¹R¹²E²(Oct¹H)(Cp²H) is formed by combining[Fulvene²] and [Oct¹]⁻, followed by quenching with a proton source, forexample water.

[0078] The dianion of R¹¹R¹²E² (Oct¹H)(Cp²H) is formed by treatment withalkali metal-alkyls or Grignard reagents in a solvent:[R¹¹R¹²E²(Oct¹)(Cp²)]⁻². Reaction of this dianion with MX_(n+2) in asolvent produces compound (III), which is isolated according to knownmethods.

EXAMPLES

[0079] 1. Polymerization Catalysts

[0080] Unless otherwise noted, all reactions and procedures are carriedout under an inert atmosphere of argon or nitrogen using standard glovebox, Schlenk and high vacuum line techniques. Solvents are driedaccording to standard procedures.

Examples 1-12

[0081] Examples 1-12 describe the synthesis of catalyst systems designedto produce elastomeric polymers, and particularly describe the synthesisof elastomeric polypropylenes.

Example 1

[0082] Preparation of 1.

[0083] The synthesis of 1 was performed as described in theliterature.[9, 10]

Example 2

[0084] Preparation of 2.

[0085] 6,6′-(tricyclo[3.3.1.1]decane)fulvene (adamantylfulvene).(Synthesis modified from reference 20) Pyrrolidine (10.0 mL, 0.116 mol)was syringed into a solution of 2-adamantanone (25.00 g, 0.1664 mol) andcyclopentadiene (30.0 mL, 0.364 mol) in 250 mL of methanol. The reactionwas stirred for 92 hours before the yellow precipitate was collected bysuction filtration, rinsed with a small volume of methanol and dried invacuo. 25.71 grams (77.9%) of adamantylfulvene were isolated. MS (GC-MS)m/z 198.3 (M⁺). ¹H NMR (CDCl₃): δ 1.93-2.08, 3.29 (m, 14H, adamantyl-H),6.52, 6.60 (m, 4H, fulvene-H). ¹³C NMR (CDCl₃): δ 28.30, 37.05, 37.35,40.25 (adamantyl-C), 119.47, 130.47 (fulvene-CH₁), 135.81, 167.38(fulvene-CH₀). Elemental analysis calculated for C₁₅H₁₈: C, 90.85; H,9.15. Found: C, 90.20, 90.22; H, 8.39, 8.50.

[0086] 2-adamantylcyclopentadiene. 6.00 grams (30.3 mmol) ofadamantylfulvene were dissolved in 30 mL of tetrahydrofuran and thissolution added over 30 minutes to a stirred slurry of LiAlH₄ (1.40 g,0.0369 mol) at 0° C. After 5 hours of stirring at room temperature, thereaction was cooled to 0° C. and quenched by slow addition of 20 mL ofsaturated NH₄Cl solution. Then 300 mL H₂O, 25 mL concentrated HCl, and50 mL diethyl ether were added, the organic layer isolated, and theaqueous layer extracted with additional diethyl ether (3×50 mL). Thecombined organic layers were dried over MgSO₄, filtered, and rotavappedto give the product, 2-adamantylcyclopentadiene, in quantitative yieldas a light yellow oil. MS (GC-MS) m/z 200.3 (M⁺).

[0087] 3-(2-adamantyl)-6,6-dimethylfulvene. To2-adamantylcyclopentadiene (6.06 g, 30.3 mmol) was added 50 mL methanol,50 mL ethanol, 20 mL tetrahydrofuran, 36 mL acetone (0.49 mol) and 0.5mL pyrrolidine (0.006 mol). After stirring for 48 hours, 5 mL of aceticacid were injected, followed by 200 mL H₂O and 200 mL diethyl ether. Theorganic layer was isolated and the aqueous layer extracted with diethylether (3×40 mL). The combined organic layers were extracted with H₂O(3×25 mL) and with 10% aqueous NaOH (3×25 mL), dried over MgSO₄,filtered and rotavapped. The obtained yellow solid was further purifiedby overnight Soxhlet extraction by 150 mL methanol. The precipitate inthe filtrate was isolated by filtration at 0° C., and in vacuo drying:4.54 g (62.5%) of 3-(2-adamantyl)-6,6-dimethylfulvene, as a yellowpowder. Elemental analysis calculated for C₁₈H₂₄: C, 89.94; H, 10.06.Found: C, 82.23, 82.23; H, 8.78, 8.82.

[0088] Me₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)H₂. 10.5 mL of an n-butyllithiumsolution (1.6 M in hexanes, 0.0168 mol) were syringed into a solution offluorene (2.77 g, 0.0166 mol) in 60 mL tetrahydrofuran. After stirringfor 5 hours, a solution of 3-(2-adamantyl)-6,6-dimethylfulvene (4.00 g,0.0166 mol) in 40 mL tetrahydrofuran was injected over 2 minutes. Afterstirring for 20 hours, 60 mL of a saturated NH₄Cl solution were added,the organic layer isolated, and the aqueous layer extracted with diethylether (2×25 mL). The combined organic layers were dried over MgSO₄,filtered and rotavapped to give the product in quantitative yield as ayellow oil.

[0089] Me₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)Li₂. The dianion was prepared bytreating a solution of Me₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)H₂ (6.77 g, 16.6mmol) in 75 mL diethyl ether with 22.0 mL of n-butyllithium solution(1.6 M in hexanes, 0.0352 mol) at 0° C. After stirring for 21 hours, thesolvent was removed by vacuum transfer and 50 mL of petroleum ether werecondensed in. The dilithio salt was isolated by filtration and in vacuodrying in quantitative yield as an orange powder.

[0090] Me₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)ZrCl₂ (2). 2.00 grams ofMe₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)Li₂ (0.00478 mol) and 1.114 g ZrCl₄(0.00478 mol) were combined in a swivel frit apparatus. 40 mL ofpetroleum ether were condensed in at −78° C. This was allowed to warmslowly to room temperature before solvent removal after 14 hours ofstirring. 40 mL of methylene chloride were condensed in and removed inorder to quench unreacted ligand. Then the orange solid was extracted inthe swivel frit with 50 mL of refluxing diethyl ether. Two crops wereobtained for a total of 1.502 grams (55.5%) of 2 as an orange powderfollowing collection at 0° C. and in vacuo drying. MS (LC-MS) m/z 566.5(M⁺). ¹H NMR (C₆D₆): δ 1.36-2.04 (m, 14H, adamantyl-H), 1.84, 1.86 (s,6H, C(CH₃)₂), 3.32 (s, 1H, 2-H-adamantyl), 5.44, 5.48, 6.18 (m, 3H,Cp-H), 6.95, 7.03, 7.29, 7.34 (t, 3J_(HH)=7.7, 7.7, 8.0, 8.0 Hz, 4H,Flu-H), 7.41, 7.49, 7.84, 7.84 (d, ³J_(HH)=8.8, 9.1, 7.7, 7.7 Hz, 4H,Flu-H). ¹³C NMR (CD₂Cl₂): δ 28.58, 28.65 (C-(CH₃)₂), 27.90, 27.93,31.98, 32.41, 32.62, 32.66, 37.84, 38.50, 38.66, 43.83 (adamantyl-C),102.56, 103.02, 116.65 (Cp-CH₁), 123.41, 123.67, 124.61, 124.67, 124.76,124.83, 128.81, 128.81 (Flu-CH₁), 139.93 (9-Flu-C),CH₀ not determined.Elemental analysis calculated for C₃₁H₃₂Zr₁Cl₂: C, 65.70; H, 5.69.Found: C, 63.46, 61.93; H, 5.57, 5.42.

Example 3

[0091] Preparation of 3.

[0092] Me₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)HfCl₂ (3). 2.00 grams ofMe₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)Li₂ (4.78 mmol) and 1.531 g HfCl₄ (4.78mol) were combined in a 100 mL flask equipped with a 180° needle valve.50 mL of petroleum ether were condensed in at −78° C. This was allowedto warm slowly to room temperature before solvent removal after 47 hoursof stirring. 20 mL of methylene chloride were condensed in and removedin order to quench unreacted ligand. Then the yellow solid was extractedin cellulose extraction thimble with 150 mL of refluxing methylenechloride for 48 hours. Solvent was removed from the filtrate and 30 mLdiethyl ether were condensed in. The yellow solid was collected on thefrit and dried in vacuo: 1.771 g (56.7%). MS (LC-MS) m/z 654.7 (M⁺). ¹HNMR (C₆D₆): δ 1.11-2.04 (m, 14H, adamantyl-H), 1.85, 1.88 (s, 6H,C(CH₃)₂), 3.37 (s, 1H, 2-H-adamantyl), 5.40, 5.43, 6.12 (m, 3H, Cp-H),6.94, 7.01, 7.27, 7.33 (t, ³J_(HH)=7.0, 7.7, 7.0, 7.3 Hz, 4H, Flu-H),7.46, 7.55, 7.84, 7.84 (d,3J_(HH)=8.8, 8.8, 8.4, 8.4 Hz, 4H, Flu-H). ¹³CNMR (CD₂Cl₂): δ 28.82, 28.88 (C-(CH₃)₂), 27.90, 27.90, 32.08, 32.40,32.65, 32.70, 37.86, 38.53, 38.68, 43.77 (adamantyl-C), 99.90, 100.22,115.73 (Cp-CH₁), 123.16, 123.42, 124.27, 124.42, 124.54, 124.66, 128.61,128.64 (Flu-CH ₁), 138.42 (9-Flu-C),CH₀ not determined. Elementalanalysis calculated for C₃,H-₃₂Hf₁Cl₂: C, 56.93; H, 4.93. Found: C,54.80; H, 4.97.

Example 4

[0093] Preparation of 4.

[0094] adamantylfulvene. (Synthesis modified from reference 20)2-adamantanone (40.22 g, 267.7 mmol), methanol (200 mL), cyclopentadiene(51.0 mL, 618.9 mmol), and pyrrolidine (20.0 mL, 239.6 mmol) were addedto a 1 liter round bottom flask. After stirring for 70 hours, the yellowprecipitate was collected by suction filtration and washed with 50 mLmethanol. After in vacuo drying, 45.59 grams adamantylfulvene wereobtained (85.9%). MS (GC-MS) m/z 198.3 (M⁺).

[0095] 2-adamantylcyclopentadiene. A 500 mL argon-purged round bottomflask was charged with LiA1H₄ (8.20 g, 216 mmol) and 100 mLtetrahydrofuran. Adamantylfulvene (30.00 g, 151.3 mmol) was added viasolid addition funnel, followed by another 100 mL tetrahydrofuran over 2minutes at 0° C. After stirring for 22 hours at room temperature, thereaction was cooled to 0° C. and 100 mL water were added dropwise over60 minutes. Then, 100 mL concentrated aqueous HCl in 300 mL water and 50mL diethyl ether were added. The organic layer was isolated and theaqueous layer extracted with diethyl ether (3×50 mL). The combinedorganic layers were dried over MgSO₄, filtered, and rotavapped to give30.30 g of product in quantitative yield. MS (GC-MS) m/z 200.3 (M⁺).

[0096] 3-(2-adamantyl)-6,6-diphenylfulvene. A 250 mL round bottom flaskwas charged with 2-adamantylcyclopentadiene (10.24 g, 51.13 mmol),benzophenone (9.32 g, 51.13 mmol) and 100 mL absolute ethanol. Once thesolids had dissolved, sodium methoxide (5.00 g, 92.6 mmol) was added andthe reaction was stirred for five days. The orange precipitate wascollected by suction filtration and washed with 50 mL ethanol. The airdried product was stirred in 100 methanol overnight and the solid wascollected by suction filtration and washed with 50 mL methanol. Dryingin vacuo for several hours provided 13.32 grams of desired product(71.5%). MS (GC-MS) m/z 364.5 (M⁺). Elemental analysis calculated forC₂₈H₂₈: C, 92.26; H, 7.74. Found: C, 87.05; H, 6.92.

[0097] Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)H₂. In the glove box, a 250 mLround bottom flask was charged with 3-(2-adamantyl)-6,6-diphenylfulvene(6.000 g, 16.46 mmol) and fluorenyllithium diethyl ether adduct (4.054g, 16.46 mmol). This was equipped with a 180° needle valve and 100 mL ofdiethyl ether were condensed into the reaction vessel. After stirring atroom temperature for 7 days, 60 mL of aqueous NH₄Cl and 50 mL water wereslowly added. After 2 hours, the solid that formed was collected byfiltration and washed with 40 mL diethyl ether. The crude, wet productwas dissolved in 250 mL tetrahydrofuran, dried over MgSO₄, filtered,rotavapped, and dried in vacuo to give 2.834 grams of a waxy solid asthe product (32.4%). MS (GC-MS) m/z 530.6 (M⁺).

[0098] Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)ZrCl₂ (4). 2.834 grams ofPh₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)H₂ (5.340 mmol) were combined withLiCH₂(trimethylsilane) (1.006 g, 10.68 mmol) in a 250 mL round bottomflask. 50 mL of tetrahydrofuran were condensed in and this was stirredat room temperature for 17 hours, when the solvent was removed. In theglove box, zirconium tetrachloride (1.245 g, 5.343 mmol) was added. 60mL of petroleum ether were condensed in and the reaction stirred at roomtemperature for 52 hours. Solvent was removed and 20 mL ofdichloromethane were condensed in, stirred, and removed. Then, 50 mL ofdiethyl ether were condensed in, stirred, and removed. The solid wasextracted overnight in a cellulose extraction thimble with 150 mLmethylene chloride. The obtained solution was filtered through a frit.Solvent was removed, 15 mL of diethyl ether were condensed in, and theorange solid was broken up, collected at 0° C., and dried in vacuo togive 0.778 grams of product 3 (21.1%). MS (LC-MS) m/z 690.9 (M⁺).Elemental analysis calculated for C₄₁H₃₆Zr₁Cl₂: C, 71.28; H, 5.25.Found: C, 68.78; H, 5.21.

Example 5

[0099] Alternate Preparation of 4.

[0100] adamantylfulvene. (Synthesis modified from reference 20)2-adamantanone (45.00 g, 299.6 mmol), methanol (200 mL), cyclopentadiene(60.0 mL, 728 mmol), and pyrrolidine (20.0 mL, 240 mmol) were added to a1 liter round bottom flask. After stirring for 77 hours, the yellowprecipitate was collected by suction filtration and washed with 50 mLmethanol. After in vacuo drying, 49.56 grams adamantylfulvene wereobtained (83.4%). MS (GC-MS) m/z 198.3 (M⁺).

[0101] 2-adamantylcyclopentadiene. A 500 mL argon-purged round bottomflask was charged with LiAlH₄ (9.00 g, 237 mmol) and 400 mL diethylether. Adamantylfulvene (31.05 g, 156.6 mmol) was added as solid over 2minutes at 0° C. After stirring for 15 hours at room temperature, thereaction was cooled to 0° C. and 60 mL water were added dropwise over 2hours, along with 300 mL diethyl ether. The alumina residue was removedby gravity filtration and rinsed with an additional 100 mL diethylether. The organic layer was rotavapped to give 30.18 g of product(96.2%) as a light yellow oil.

[0102] 3-(2-adamantyl)-6,6-diphenylfulvene. A 500 mL round bottom flaskcontaining 2-adamantylcyclopentadiene (30.18 g, 150.7 mmol) was addedbenzophenone (27.50 g, 150.9 mmol) and 300 mL absolute ethanol. Once thesolids had dissolved, sodium methoxide (15.00 g, 278 mmol) was added andthe reaction was stirred for six days. The orange precipitate wascollected by suction filtration and the air dried product was thenstirred in 100 methanol for two days before the solid was collected bysuction filtration and washed with 100 mL methanol. Drying in vacuo fortwo days provided 25.72 grams of desired product (46.8%). And secondcrop was obtained: 6.08 grams (57.9% for both crops). MS (GC-MS) m/z364.5 (M⁺). ¹H NMR (CDCl₃): δ 1.52-2.23 (m, 14H, adamantyl-H), 2.80 (s,1H, 2-H-adamantyl), 7.30-7.40 (m, 12H, phenyl-H), 6.05 (m, 1H,fulvene-H), 6.29, 6.59 (d, ³J_(HH)=3.4, 3.7 Hz, 2H, fulvene-H). ¹³C NMR(CDCl₃): δ 28.14, 28.14, 31.21, 31.21, 32.72, 32.72, 38.06, 38.92, 38.92(adamantyl-C), 45.20 (2-C-adamantyl), 118.16, 125.01, 133.10(fulvene-CH₁), 127.68, 127.68, 127.77, 127.77, 128.31, 128.31, 132.02,132.02, 132.08, 132.08 (phenyl-CH₁), 141.70, 141.70 (ipso-C), 144.39,148.69, 152.27 (fulvene-CH₀). Elemental analysis calculated for C₂₈H₂₈:C, 92.26; H, 7.74. Found: C, 83.42; H, 6.59.

[0103] Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)H₂. In the glove box, a 250 mLround bottom flask was charged with 3-(2-adamantyl)-6,6-diphenylfulvene(20.00 g, 54.87 mmol) and fluorenyllithium diethyl ether adduct (13.51g, 54.86 mmol). This was equipped with a 180° needle valve and 150 mL ofdiethyl ether were condensed into the reaction vessel. After stirring atroom temperature for 2 days and at reflux for 7 days, 60 mL H₂O wereslowly added. After 3 hours, the solid that formed was collected byfiltration. The air dried product was combined with 100 mL diethyl etherand stirred for 1 hour before collection by suction filtration, rinsingwith 25 mL diethyl ether, and in vacuo drying: 14.30 (49.1%). MS (GC-MS)m/z 530.6 (M⁺). Elemental analysis calculated for C₄₁H₃₈: C, 92.78; H,7.22. Found: C, 85.14, 84.89; H, 6.04, 6.08.

[0104] Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)Li₂. A large swivel frit wascharged with Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃Hg)H₂ (14.00 g, 26.38 mmol)and evacuated before 150 mL of diethyl ether were condensed in. 35.0 mLof n-butyllithium in hexanes (1.6 M, 56.0 mmol) were syringed in at roomtemperature over 5 minutes. The reaction was stirred at room temperaturefor 22 hours and at 40° C. for 5 hours. The orange precipitate wascollected and dried in vacuo: 11.44 g (79.9%).

[0105] Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)ZrCl₂ (4). In the glove box,4.657 grams of Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)Li₂ (8.582 mmol) werecombined with ZrCl₄ (2.000 g, 8.583 mmol) in a 100 mL round bottomflask. This was equipped with a 180° needle valve and 60 mL petroleumether were condensed in by vacuum transfer at −78° C. The vessel wasallowed to warm slowly, and after 46 hours of stirring, solvent wasremoved. The solid was extracted for two days in a cellulose extractionthimble with 150 mL methylene chloride. The obtained solution wasfiltered through a frit and condensed to 15 mL. After sitting for 1hour, the formed precipitate was collected on the frit and dried invacuo: 2.443 g of product 3 were obtained (41.2%). MS (LC-MS) m/z 690.7(M⁺). ¹H NMR (C₆D₆): δ 1.46-2.10 (m, 14H, adamantyl-H), 3.36 (s, 1H,2-H-adamantyl), 5.73, 5.74 (s, 2H, Cp-H), 6.28 (t, ³J_(HH)=2.9 Hz, 1H,Cp-H), 6.93, 6.97, 7.02, 7.04, 7.12, 7.14 (t,3J_(HH)=7.3, 7.3, 7.4, 7.4,7.3, 6.6 Hz, 6H, phenyl-H, 7.59, 7.60, 7.82, 7.95 (d, ³J_(HH)=8.1, 8.1,8.1, 8.4 Hz, 4H, phenyl-H), 6.49, 6.55, 7.90, 7.90 (d, ³J_(HH)=8.8, 8.8,8.4, 8.4 Hz, 4H, Flu-H), 6.71, 6.77, 7.28, 7.33 (t, ³J_(HH)=7.0, 7.0,7.4, 7.4 Hz, 4H, Flu-H). ¹³C NMR (CD₂Cl₂): δ 27.90, 28.03, 32.30, 32.48,32.51, 32.72, 37.88, 38.48, 38.64 (adamantyl-C), 43.88 (2-C-adamantyl),104.23, 104.57, 116.06 (Cp-CH₁), 121.30, 121.43, 122.98, 123.28(Flu-CH₀), 123.82, 124.02, 124.53, 124.68, 124.14, 125.28, 126.65,126.65, 127.20, 127.26, 128.06, 128.06, 129.04, 129.04, 129.13, 129.13,129.26, 129.39 (phenyl- and Flu-CH₁), 139.39 (9-Flu-C), 145.01, 145.11(ipso-C), other CHO not determined. Elemental analysis calculated forC₄₁H₃₆Zr₁Cl₂: C, 71.28; H, 5.25. Found: C, 63.48, 63.71; H, 4.46, 4.57.

Example 6

[0106] Preparation of 5.

[0107] Ph₂C(3-(2-adamantyl)C₅H3)(C₁₃H₈)HfCl₂ (5). In the glove box,3.388 grams of Ph₂C(3-(2-adamantyl)C₅H₃)(C₁₃H₈)Li₂ (6.244 mmol, preparedas given in the alternate preparation of 3) were combined with HfCl₄(2.000 g, 6.244 mmol) in a 100 mL round bottom flask. This was equippedwith a 180° needle valve and 60 mL petroleum ether were condensed in byvacuum transfer at −78° C. The vessel was allowed to warm slowly, andafter 30 hours of stirring, solvent was removed. The solid was extractedovernight in a cellulose extraction thimble with 150 mL methylenechloride. The obtained solution was filtered through a frit andcondensed to 30 mL. After sitting for 1 hour, the formed precipitate wascollected on the frit and dried in vacuo: 1.547 g of product 5 wereobtained (31.8%). A second crop was obtained from toluene: 1.237 g(57.3% for both crops). MS (LC-MS) m/z 778.8 (M⁺). ¹H NMR (C₆D₆): δ1.45-2.09 (m, 14H, adamantyl-H), 3.41 (s, 1H, 2-H-adamantyl), 5.68, 5.69(s, 2H, Cp-H), 6.21 (t, ³J_(HH)=3.0 Hz, 1H, Cp-H), 6.93, 6.98, 7.02,7.04, 7.12, 7.14 (t, ³J_(HH)=7.3, 7.3, 7.7, 7.7, 8.0, 8.0 Hz, 6H,phenyl-H), 7.60, 7.60, 7.83, 7.96 (d, ³J_(HH)=7.4, 7.4, 8.1, 7.7 Hz, 4H,phenyl-H), 6.54, 6.60, 7.89, 7.89 (d, ³J_(HH)=8.8, 9.2, 8.4, 8.4 Hz, 4H,Flu-H), 6.71, 6.77, 7.26, 7.31 (t, ³J_(HH)=7.7, 7.7, 7.3, 7.0 Hz, 4H,Flu-H). ¹³C NMR (CD₂Cl₂): δ 27.91, 28.01, 32.42, 32.47, 32.59, 32.72,37.93, 38.53, 38.67 (adamantyl-C), 43.83 (2-C-adamantyl), 101.61,101.92, 115.20 (Cp-CH₁), 120.19, 120.27, 121.51, 121.87 (Flu-CH₀),123.62, 123.83, 124.45, 124.57, 124.79, 124.92, 126.68, 126.68, 127.18,127.24, 127.84, 127.85, 128.99, 128.99, 129.12, 129.12, 129.29, 129.41(phenyl- and Flu-CH₁), 137.91 (9-Flu-C), 145.28, 145.38 (ipso-C), otherCHo not determined. Elemental analysis calculated for C₄₁H₃₆Hf₁Cl₂: C,63.29; H, 4.66. Found: C, 66.36, 66.16; H, 4.66, 4.69.

Example 7

[0108] Preparation of 6

[0109] norbornylfulvene. Norcamphor (10.00 g, 90.8 mmol) and sodiummethoxide (12.0 g, 222 mmol) and 100 mL methanol were added to a 250 mLflask. The solids were dissolved before addition of cyclopentadiene(12.0 g, 182 mmol). After stirring for 68 hours, 200 mL water and 100 mLdiethyl ether were added to the deep red solution. The organic layer wasisolated and the aqueous layer was extracted with diethyl ether (3×50mL). The combined organic layers were dried over MgSO₄, filtered androtavapped to yield the crude product in quantitative yield.

[0110] norbornylcyclopentadiene. A solution of norbornylfulvene (14.37g, 90.8 mmol) dissolved in 100 mL tetrahydrofuran was cooled to 0° C.before LiAlH₄ (5.00 g, 132 mmol) was added over 2 minutes. Afterstirring at room temperature for 17 hours, the reaction was cooled to 0°C. and 100 mL water were added dropwise over 1 hour. Then, 200 mLwater/50 mL concentrated aqueous HCl and 100 mL diethyl ether wereadded. The organic layer was isolated and the aqueous layer wasextracted with diethyl ether (3×50 mL). The organic layers were driedover MgSO₄, filtered, and rotavapped to provide the crude product as alight yellow oil in quantitative yield.

[0111] 3-(2-norbornyl)-6,6-dimethylfulvene. Sodium methoxide (4.00 g,74.0 mmol) was added to a solution of norbornylcyclopentadiene (8.00 g,49.9 mmol) in 50 mL methanol. Acetone (15.8 g, 270 mmol) was added andthe reaction stirred for 48 hours when 200 mL water and 100 mL diethylether were added. The organic layer was isolated and the aqueous layerwas extracted with diethyl ether (4×50 mL). The organic layers weredried over MgSO₄, filtered, and rotavapped to provide the crude productas a yellow oil, which was purified by in vacuo drying and passingthrough a short column of alumina: 8.18 g (81.8%). MS (GC-MS) m/z 200.3(M⁺).

[0112] Me₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)H₂. A 250 mL flask was chargedwith fluorene (3.32 g, 20.0 mmol), evacuated, and backfilled with argonbefore 60 mL tetrahydrofuran and 13.0 mL n-butyllithium in hexanes (1.6M, 20.8 mmol) were syringed in. The orange solution was stirred for 30minutes before 3-(2-norbornyl)-6,6-dimethylfulvene (4.00 g, 20.0 mmol)were syringed in. Following an additional 20 hours, the stirred reactionwas quenched by addition of 60 mL aqueous NH₄Cl. The organic layer wasisolated and the aqueous layer extracted with diethyl ether (2×25 mL).The combined organic layers were dried over MgSO₄, filtered, rotavapped,and dried in vacuo to give 7.32 grams of product as a light yellow oilin quantitative yield.

[0113] Me₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)Li₂. A swivel frit was chargedwith Me₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)H₂ (7.32 g, 20.0 mmol) andevacuated before 50 mL of diethyl ether were condensed in. To thesolution was added 26.0 mL of n-butyllithium in hexanes (1.6 M, 41.6mmol) at 0° C. over 1 minute. The reaction was stirred at roomtemperature for 18 hours before the solvent was removed and 50 mLpetroleum ether were added by vacuum transfer. After stirring, thesolvent was decanted from the red oil and the oil dried in vacuo toprovide the product in quantitative yield as a red-yellow powder.

[0114] Me₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)ZrCl₂ (6). In the glove box, 2.44grams of Me₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)Li₂ (6.44 mmol) were combinedwith ZrCl₄ (1.50 g, 6.44 mmol) in a 100 mL round bottom flask. This wasequipped with a 180° needle valve and 40 petroleum ether were condensedin by vacuum transfer at −78° C. The vessel was allowed to warm slowly,and after 24 hours of stirring, solvent was removed. Then 30 mL ofdichloromethane were added and removed, followed by addition and removalof 30 mL diethyl ether. The solid was extracted overnight in a celluloseextraction thimble with 150 mL of diethyl ether. The filtrate volume wasreduced to 30 mL and the precipitated product was collected on a swivelfrit and dried in vacuo: 1.26 grams of 5 (37.2%) in a 54:46diastereomeric ratio. MS (LC-MS) m/z 526.6 (M⁺). Major diastereomer(54%): ¹H NMR (C₆D₆): δ 1.01-1.35 (m, 8H, norbornyl-H), 1.89-2.07 (m,2H, norbornyl-H), 1.82, 1.83 (s, 6H, C(CH₃)₂), 3.20 (m, 1H,2-H-norbornyl), 5.42, 5.45, 6.09 (t, ³J_(HH)=3.3, 3.3, 2.9 Hz, 3H,Cp-H), 7.00, 7.03, 7.35, 7.35 (t, ³J_(HH)=7.7, 7.7, 7.3, 7.3 Hz, 4H,Flu-H), 7.45, 7.47, 7.84, 7.86 (d, ³J_(HH)=8.1, 8.8, 8.4, 8.4 Hz, 4H,Flu-H). ¹³C NMR (CD₂Cl₂): δ 23.52, 29.71, 34.05, 37.25, 40.13, 41.00,43.61, (norbornyl-C), 28.58, 28.66 (CH3), 40.51 (CH₃CCH₃), 65.70, 79.12,114.31, 122.59, 122.88, 123.15, 140.29 (Cp- and Flu-CH₀), 102.73,103.79, 116.17 (Cp-CH₁), 123.49, 123.58, 124.64, 124.74, 124.80, 124.84,128.76, 128.84 (Flu-CH₁). Minor diastereomer (46%): ¹H NMR (C₆D₆): δ1.01-1.35 (m, 8H, norbornyl-H), 1.89-2.07 (m, 2H, norbornyl-H), 1.79,1.83 (s, 6H, C(CH₃)₂), 3.13 (m, 1H, 2-H-norbornyl), 5.23, 5.54, 6.04 (t,³J_(HH)=3.0, 2.9, 2.9 Hz, 3H, Cp-H), 6.98, 7.03, 7.30, 7.30 (t,J_(HH)=7.7, 7.7, 7.7, 7.7 Hz, 4H, Flu-H), 7.43, 7.45, 7.83, 7.84 (d,³J_(HH)=8.4,8.1,8.4,8.4 Hz,4H, FLu-H). ¹³C NMR (CD₂Cl₂): δ 23.68, 29.80,34.17, 36.97, 39.39, 41.53, 43.29, (norbornyl-C), 28.58, 28.58 (CH3),40.55 (CH₃CCH₃), 65.65, 79.02, 113.27, 122.55, 122.88, 123.40, 138.57(Cp- and Flu-CH₀), 102.31, 103.69, 117.44 (Cp-CHi), 123.37,123.71,124.64, 124.74,124.80,124.84, 128.84, 128.92 (Flu-CH₁). Elementalanalysis calculated for C₂₈H₂₈Zr₁Cl₂: C, 63.86; H, 5.36. Found: C,61.78, 61.58; H, 5.03, 5.23.

Example 8

[0115] Preparation of 7.

[0116] 3-(2-norbornyl)-6,6-diphenylfulvene. A 500 mL round bottom flaskwas charged with a solution of norbornylcyclopentadiene (7.39 g, 46.1mmol) and benzophenone (8.41 g, 46.2 mmol) in 100 mL absolute ethanol.NaOMe (5.50 g, 102 mmol) was added and the orange solution was stirredfor 61 days before 100 mL H₂O and 100 mL diethyl ether were added. Theorganic layer was isolated and the aqueous layer was extracted withdiethyl ether (2×50 mL). The combined organic layers were dried overMgSO₄, filtered, and rotavapped to provide 14.88 grams of red oilymaterial. This was subjected to Kugelrohr distillation under high vacuumat 80-100° C., leaving behind 9.30 grams of red oil. This wasKugelrohred at 100-160° C. to afford 7.05 grams of product as a viscousred oil (47.1%).

[0117] Ph₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)H₂. In the glove box, a 100 mLround bottom flask was charged with 3-(2-norbornyl)-6,6-diphenylfulvene(7.05 g, 21.7 mmol) and fluorenyllithium diethyl ether adduct (5.35 g,21.7 mmol). This was equipped with a 180° needle valve and 60 mL ofdiethyl ether were condensed into the reaction vessel. After stirringwith intermittent heating by a warm water bath for 11 days, 20 mL of H₂Owere slowly added. The precipitate that eventually formed was collectedby suction filtration and dried in vacuo: 6.136 grams (57.6%). MS(GC-MS) m/z 490.6 (M⁺). Elemental analysis calculated for C₃₈H₃₄: C,93.02; H, 6.98. Found: C, 78.93, 79.39; H, 5.27, 5.25.

[0118] Ph₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)Li₂. A swivel frit was chargedwith Ph₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)H₂ (6.136 g, 12.50 mmol) andevacuated before 60 mL of diethyl ether were condensed in. To the whiteslurry was added 17.0 mL of n-butyllithium in hexanes (1.6 M, 27.2 mmol)at room temperature over 3 minutes, giving a homogeneous solution, whichbegan precipitation after 20 minutes. The reaction was stirred at roomtemperature for 15 hours and the yellow precipitate was collected anddried in vacuo to yield the product in quantitative yield.

[0119] Ph₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)ZrCl₂ (7). In the glove box, 3.24grams of Ph₂C(3-(2-norbornyl)C₅H₃)(C₁₃H₈)Li₂ (6.44 mmol) were combinedwith ZrCl₄ (1.50 g, 6.44 mmol) in a 100 mL round bottom flask. This wasequipped with a 180° needle valve and 60 petroleum ether were condensedin by vacuum transfer at −78° C. The vessel was allowed to warm slowly,and after 24 hours of stirring, solvent was removed. The solid wasextracted overnight in a cellulose extraction thimble with 150 mLmethylene chloride. The solvent was removed and the solid redissolved in75 mL toluene and 25 mL methylene chloride. The obtained solution wasfiltered through a frit, all solvent was removed, and 40 mL toluene werecondensed in. The orange solid was broken up, stirred, collected on thefrit and dried in vacuo to afford the product 5 in a 64:36diastereomeric ratio: 1.81 grams (43.2%). MS (LC-MS) ml/z 650.5 (M⁺).Major diastereomer (64%): ¹H NMR (C₆D₆): δ 0.99-1.40 (m, 8H,norbornyl-H), 1.83-2.09 (m, 2H, norbornyl-H), 3.09 (m, 1H,2-H-norbornyl), 5.53, 5.71, 6.19 (t, ³J_(HH)=3.0, 2.9, 2.6 Hz, 3H,Cp-H), 6.91-7.13 (m, 6H, phenyl-H), 7.56, 7.56, 7.75, 7.75 (d,³J_(HH)=8.1, 8.1, 7.7, 7.7 Hz, 4H, phenyl-H), 6.49, 6.53, 7.89, 7.89 (d,³J_(HH)=8.8, 8.8, 8.1, 8.1 Hz, 4H, Flu-H), 6.78, 6.81, 7.31, 7.33 (t,³J_(HH)=7.7, 7.7, 8.4, 8.4 Hz, 4H, Flu-H). ¹³C NMR (CD₂Cl₂): δ 23.91,29.78, 34.42, 37.34, 40.19, 41.64, 43.41 (norbornyl-C), 58.33 (PhCPh),78.20, 109.96, 121.26, 121.61, 123.10, 123.30, 138.11, 145.00,145.00(Cp-, phenyl-, and Flu-CH₀), 104.38, 105.22, 115.76 (Cp-CH₁),123.97, 123.97, 124.61, 124.69, 125.30, 125.30, 126.68, 126.73, 127.26,127.31, 128.03, 128.11, 128.23, 129.05, 129.08, 129.17, 129.29, 129.36(phenyl- and Flu-CH₁). Minor diastereomer: ¹H NMR (C₆D₆): δ 0.99-1.40(m, 8H, norbornyl-H), 1.83-2.09 (m, 2H, norbornyl-H), 3.19 (m, 1H,2-H-norbornyl), 5.66, 5.80, 6.11 (t, ³J H=2.9, 2.9, 2.6 Hz, 3H, Cp-H),6.91-7.13 (m, 6H, phenyl-H), 7.58, 7.60, 7.79, 7.79 (d, ³J_(HH)=8.1,8.1, 8.0, 8.0 Hz, 4H, phenyl-H), 6.45, 6.58, 7.91, 7.91 (d, ³J_(HH)=8.8,8.8, 8.1, 8.1 Hz, 4H, Flu-H), 6.76, 6.78, 7.29, 7.33 (t, ³J_(HH)=7.7,7.7, 8.4, 8.4 Hz, 4H, Flu-H). ¹³C NMR (CD₂Cl₂): δ 23.88, 29.66, 34.14,37.02, 39.45, 40.93, 44.04 (norbornyl-C), 58.33 (PhCPh), 78.43, 108.97,121.37, 121.50, 123.00, 123.30, 139.95, 144.92, 145.20 (Cp-, phenyl-,and Flu-CH₀), 103.63, 105.16, 116.84 (Cp-CH₁), 123.67, 124.07, 124.61,124.74, 125.13, 125.39, 126.57, 126.64, 127.26, 127.31, 128.09, 128.11,128.18, 129.08, 129.17, 129.29, 129.36, 129.45 (phenyl- and Flu-CH₁).Elemental analysis calculated for C₃₈H₃₂Zr₁Cl₂: C, 70.13; H, 4.96.Found: C, 71.10, 70.50; H, 4.71, 4.64.

Example 9

[0120] Preparation of 8.

[0121] 3,3,5,5-tetramethylcyclohexylfulvene. Hexane washed sodiumspheres (2.40 g, 104 mmol) were slowly added to 100 mL absolute ethanol.The sodium had fully reacted before cyclopentadiene (6.0 mL, 72.6 mmol)and 3,3,5,5-tetramethylcyclohexanone (10.0 mL, 57.1 mmol) were added.After 30 hours, the reaction was poured into 200 mL water and 100 mLdiethyl ether were added. The organic layer was isolated and the aqueouslayer was extracted with diethyl ether (3×50 mL). The combined organiclayers were extracted with water (3×50 mL), dried over MgSO₄, filtered,and rotavapped to produce the product in quantitative yield as a yellowoil. MS (GC-MS) m/z 202.3 (M⁺). ¹H NMR (CDCl₃): δ 0.97 (s, 12H, CH₃),1.04 (s, 2H, CH₂), 2.39 (s, 4H, CH₂), 6.52, 6.52 (m, 4H, fulvene-H).1-(cyclopentadienyl)-3,3,5,5-tetramethylcyclohexane. A 500 mL flask wascharged with LiAlH₄ (2.50 g, 65.9 mmol) and 200 mL tetrahydrofuran. Anaddition funnel containing 3,3,5,5-tetramethylcyclohexylfulvene (11.89g, 58.8 mmol) dissolved in 50 mL tetrahydrofuran was attached. Thevessel was cooled to 0° C. before dropwise addition over 25 minutes.After 17 hours of stirring at room temperature, the vessel was cooled to0° C. and 20 mL of water were added dropwise. Then, aqueous NH₄Cl (100mL) and water (200 mL) were added before the organic layer was isolated.15 mL of concentrated aqueous HCl were added to the aqueous layer and itwas extracted with diethyl ether (3×50 mL). The combined organic layerswere dried over MgSO₄, filtered, and rotavapped to provide 11.87 gramsof product (98.8%) as a light orange oil. MS (GC-MS) m/z 204.3 (M⁺).3-(3,3,5,5-tetramethylcyclohexyl)-6,6-dimethylfulvene. A 500 mL flaskwas charged with 1-(cyclopentadienyl)-3,3,5,5-tetramethylcyclohexane(11.87 g, 58.1 mmol), 100 mL methanol, acetone (30 mL, 430 mmol), andpyrrolidine (1.0 mL, 12 mmol). After stirring for 52 hours, 5 mL ofacetic acid were added, along with 200 mL water and 100 mL diethylether. The organic layer was isolated and the aqueous layer wasextracted with diethyl ether (3×50 mL). The combined organic layers wereextracted with H₂O (3×30 mL) and 10% aqueous NaOH (3×30 mL). The organiclayer was dried over MgSO₄, filtered, rotavapped, dried in vacuo, andpushed through a short column of alumina to provide the product inquantitative yield as a yellow oil. MS (GC-MS) m/z 244.4 (M⁺).

[0122] Me₂C(3-(3,3,5,5-tetramethylcyclohexyl)C₅H₃)(C₁₃H₈)H₂. A 250 mLflask was charged with fluorene (3.69 g, 22.2 mmol), evacuated, andbackfilled with argon before 60 mL tetrahydrofuran and 14.0 mLn-butyllithium in hexanes (1.6 M, 22.4 mmol) were syringed in. Theorange solution was stirred for 2 hours before3-(3,3,5,5-tetramethylcyclohexyl)-6,6-dimethylfulvene (5.42 g, 22.2mmol) were syringed in. Following an additional 6 hours, the stirredreaction was quenched by addition of 60 mL aqueous NH₄Cl. The organiclayer was isolated and the aqueous layer extracted with diethyl ether(2×30 mL). The combined organic layers were dried over MgSO₄, filtered,and rotavapped to give 8.75 grams of product as a light yellow oil(96.1%).

[0123] Me₂C(3-(3,3,5,5-tetramethylcyclohexyl)C₅H₃)(C₁₃H₈)Li₂. A roundbottom flask containing 8.75 grams (21.3 mmol) ofMe₂C(3-(3,3,5,5-tetramethylcyclohexyl)C₅H₃)(C₁₃H₈)H₂ was attached to aswivel frit and evacuated before 75 mL of diethyl ether were condensedin. At 0° C., 28.0 mL of n-butyllithium in hexanes (1.6 M, 44.8 mmol)were syringed in over 2 minutes. After, stirring for 15 hours at roomtemperature, solvent was removed and 75 mL of petroleum ether werecondensed in. Solvent was decanted from the viscous oil and theremaining material was dried in vacuo: 8.29 g (92.0%) of product as abright orange powder.

[0124] Me₂C(3-(3,3,5,5-tetramethylcyclohexyl)C₅H₃)(C₁₃H8)ZrCl2 (8). Inthe glove box, 1.81 grams ofMe₂C(3-(3,3,5,5-tetramethylcyclohexyl)C₅H₃)(C₁₃H₈)Li₂ (4.29 mmol) werecombined with ZrCl₄ (1.00 g, 4.29 mmol) in a 100 mL round bottom flask.This was attached to a swivel frit and 50 petroleum ether were condensedin by vacuum transfer at −78° C. The vessel was allowed to warn slowly,and after 15 hours of stirring, solvent was removed. 40 mL of methylenechloride were condensed in; the solution was warmed and stirred beforesolvent removal. Then, 30 mL of diethyl ether were condensed in and theslurry was warmed and stirred. The obtained orange solid was extractedseveral times on the frit with refluxing diethyl ether before thefiltrate was condensed to 20 mL. The precipitate was collected on thefrit and dried in vacuo to afford the product 7: 0.16 grams (6.6%).Second and third crops were obtained: 0.13 g and 0.23 g (21.2% for allthree crops). MS (LC-MS) m/z 570.6 (M⁺). ¹H NMR (CD₂Cl₂): δ 0.83, 0.83,0.90, 0.99 (s, 12H, cyclohexyl(CH₃)), 0.88-1.27 (m, 6H, cyclohexyl-H),2.33, 2.35 (s, 6H, C(CH₃)₂), 2.69 (t, ³J_(HH)=12.4 Hz, 1H,1-H-cyclohexyl), 5.46, 5.69, 5.99 (t, 3J_(HH)=2.6, 3.3, 2.6 Hz, 3H,Cp-H), 7.24, 7.26, 7.51, 7.53 (t, ³J_(HH)=7.7, 7.7, 7.7, 7.5 Hz, 4H,Flu-H), 7.82, 7.86, 8.12, 8.12 (d, ³J_(HH)=8.8, 9.2, 8.4, 8.4 Hz, 4H,Flu-H). ¹³C NMR (CD₂Cl₂): δ 26.77, 27.23, 28.47, 28.52, 28.62, 28.67(CH3), 31.44 (1-cyclohexyl-C), 32.05, 39.71, 40.50, 43.45, 49.00, 52.01(cyclohexyl and MeCMe CHo and CH2), 102.69, 102.74, 115.19 (Cp-CH₁),123.56, 123.58, 123.58, 124.62, 124.73, 124.73, 124.78, 124.80(benzo-CH₁), 141.29 (9-Flu-C), CH₀, not determined. Elemental analysiscalculated for C₃₁H₃₆Zr₁Cl₂: C, 65.24; H, 6.36. Found: C, 60.96, 61.75;H, 5.53, 5.60.

Example 10

[0125] Preparation of 9.

[0126] 3,6,6-trimethylfulvene. A 1 liter flask was charged with 400 mLmethanol, methylcyclopentadiene (120.0 mL, 1.21 mol), acetone (200 mL,2.72 mol), and pyrrolidine (40.0 mL, 0.464 mol). After stirring theorange solution for 71 hours, 50 mL of acetic acid were added, followedby 1200 mL H₂O and 200 mL diethyl ether. The organic layer was isolatedand the aqueous layer was extracted with diethyl ether (5×100 mL). Thecombined organic layers were extracted with H₂O (3×30 mL) and 10%aqueous NaOH (3×30 mL). The organic layer was dried over MgSO₄, filteredand rotavapped to give 158.8 grams of a red-orange oil that wassubjected to Kugelrohr distillation under high vacuum. The first 15grams of material that distilled at room temperature was discarded andthe product was obtained from the second fraction that distilled at 50°C.: 136.58 grams (94.0%).

[0127] Me₂C(3-methyl-C₅H₃)(C₁₃H₈)H₂. A 500 mL round bottom flask wascharged with fluorene (55.32 g, 332.8 mmol). This was equipped with a180° needle valve, evacuated, and backfilled with argon before and 240mL of diethyl ether were added via syringe. 210.0 mL of n-butyllithiumin hexanes (1.6 M, 336.0 mmol) were syringed in at room temperature over20 minutes. After shaking and stirring the obtained yellow slurry for 1hour, 3,6,6-trimethylfulvene (40.00 g, 332.8 mmol) was syringed in over25 minutes, providing a clear, red solution. After stirring for 17hours, the vessel was cooled to 0° C. and 60 mL aqueous NH₄Cl solutionwere added. The slurry was filtered and the aqueous layer removed. Theobtained solid was extracted from a cellulose extraction thimble with500 mL diethyl ether/hexanes for two days. The first crop was obtainedby filtration of the cooled filtrate: 28.45 g following in vacuo drying(29.9%). The second and third crops were obtained by filtration of thechilled (−78° C.) filtrate and massed 11.86 and 1.08 grams, respectively(43.4% for all three crops). MS (GC-MS) m/z 286.3 (M⁺). Elementalanalysis calculated for C₂₂H₂₂: C, 92.26; H, 7.74. Found: C, 90.99,90.92; H, 7.21, 7.21.2,6,6-trimethyl-4-(C(methyl)₂(9-fluorenyl))-fulvene. 11.86 grams ofMe₂C(3-methyl-C₅H₃)(C₁₃H₈)H₂ (41.41 mmol) were combined with 200 mLacetone (2720 mmol) and 15.0 mL pyrrolidine (180 mmol). After stirringfor 30 minutes, a homogeneous solution is obtained and stirring isceased. The product slowly crystallized, and after 30 days the yellowcrystals were collected by filtration. These were combined with 100 mLmethanol, brought to a boil for 4 hours, and stirred overnight as thevessel cooled. Collection by suction filtration, rinsing with 25 mLmethanol, and in vacuo drying afforded 8.15 grams of the desired product(60.3%). MS (GC-MS) m/z 326.5 (M⁺). ¹H NMR (CDCl₃): δ 1.02, 1.02 (s, 6H,C(CH₃)₂Flu), 2.16, 2.25, 2.53 (s, 9H, 2,6,6-CH₃-fulvene), 4.13 (s, 1H,9-H-Flu), 5.96, 6.54 (s, 2H, 3,5-H-fulvene), 7.15, 7.31 (t, ³J_(HH)=7.4,7.4 Hz, 4H, Flu-H), 7.28, 7.70 (s, ³J_(HH)=7.3, 7.7 Hz, 4H, Flu-H). ¹³CNMR (CDCl₃): δ 19.04, 22.46, 24.53, 24.53, 25.18 (CH3), 39.38 (CH₀),55.66 (9-Flu-CH₁), 114.78, 130.54 (fulvene-CH₁), 119.30, 119.30, 126.07,126.07, 126.52, 126.52, 126.92, 126.93 (Flu-CH₁), 132.75, 133.98,140.86, 151.75 (fulyene-CH₀), 142.04, 142.04, 145.54, 145.54 (Flu-CH₀).Elemental analysis calculated for C₂₅H₂₆: C, 91.97; H, 8.03. Found: C,90.83, 91.12; H, 7.33, 7.26.

[0128] Me₂C(3-t-butyl-4-methyl-C₅H₂)(C₁₃H₈)H₂. A 250 mL round bottomflask was charged with 5.087 grams of2,6,6-trimethyl-4-(C(methyl)₂(9-fluorenyl))-fulvene (15.58 mmol). Thiswas evacuated before 100 mL diethyl ether were condensed in. 75.0 mL ofmethyllithium in diethyl ether (1.4 M, 105 mmol) were added by syringe,giving an orange homogeneous solution after 1 hour. After one month ofstirring, a small amount of orange precipitate was found. The amountslowly increased, and after 47 days total, the orange slurry was cooledto 0° C. and slowly quenched with 60 mL H₂O. The organic layer wasisolated and the aqueous layer was extracted with diethyl ether (2×25mL). The combined organic layers were dried over MgSO₄, filtered androtavapped to provide the product in quantitative yield (5.34 g) as alight yellow oil, which slowly began to crystallize.

[0129] Me₂C(3-t-butyl-4-methyl-C₅H₂)(C₁₃H8)Li₂. A round bottom flaskcontaining 5.34 grams (15.6 mmol) ofMe₂C(3-t-butyl-4-methyl-C₅H₂)(C₁₃H₈)H₂ was attached to a swivel frit andevacuated before 75 mL of diethyl ether were condensed in. At 0° C.,22.0 mL of n-butyllithium in bexanes (1.6 M, 32.5 mmol) were syringed inover 1 minute. After stirring for 15 hours at room temperature, theorange precipitate was collected and dried in vacuo: 5.37 g (97.3%).

[0130] Me₂C(3-t-butyl-4-methyl-C₅H₂)(C₁₃H₈)ZrCl₂ (9). In the glove box,2.28 grams of Me₂C(3-t-butyl-4-methyl-C₅H₂)(C₁₃H₈)Li₂ (6.44 mmol) werecombined with ZrCl₄ (1.50 g, 6.44 mmol) in a 100 mL round bottom flask.This was equipped with a 180° needle valve and 50 petroleum ether werecondensed in by vacuum transfer at −78° C. The vessel was allowed towarm slowly, and after 23 hours of stirring, solvent was removed. 30 mLof methylene chloride were condensed in; the solution was warmed andstirred before solvent removal; 30 mL of diethyl ether were condensedin; the slurry was warmed and stirred before solvent removal. Theobtained solid was extracted overnight in a cellulose extraction thimblewith 150 mL methylene chloride. The obtained solution was filteredthrough a frit, all solvent was removed, and 50 mL diethyl ether werecondensed in. The pink solid was broken up, stirred, collected on thefrit and dried in vacuo to afford the product 9: 1.60 grams (49.5%). MS(LC-MS) m/z 502.3 (M⁺). ¹H NMR (C₆D₆): δ 1.25 (s, 9H, C(CH₃)₃) 1.82,1.85 (s, 6H, C(CH₃)₂), 2.09 (s, 3H, Cp-CH₃), 5.20, 5.50 (d,3J_(HH)=3.6,3.6 Hz, 3H, Cp-H), 6.98, 6.98, 7.31, 7.31 (t,3J_(HH)=7.0, 7.0, 7.3, 7.3Hz, 4H, Flu-h), 7.41, 7.47, 7.82, 7.85 (d, 3J_(HH)=8.4, 8.4, 8.0, 8.4Hz, 4H, Flu-H). ¹³C NMR (CD₂Cl₂): δ 16.08, 28.24, 28.75 (CH3), 29.17(C(CH₃)₃), 33.52, 39.85 (CH₀), 78.40, 110.49, 121.76, 123.65, 123.79,128.00, 140.84 (Cp and Flu CH₀), 102.93, 108.11 (Cp-CH₁), 123.42,123.64, 124.45, 124.55, 124.68, 124.96, 128.33, 128.80 (Flu-CHi).Elemental analysis calculated for C₂₆H₂₈Zr₁Cl₂: C, 62.13; H, 5.61.Found: C, 60.88, 60.89; H, 4.90, 4.94.

Examples 11

[0131] Synthesis of 91

[0132] 6,6-diphenylfulvene. A 1 liter round bottom flask was chargedwith sodium methoxide (41.00 grams, 0.759 mol), ethanol (500 mL),benzophenone (125.00 grams, 0.686 mol) and cyclopentadiene (100.0 mL,1.213 mol). This was stirred for 7 days before the orange precipitatewas collected by suction filtration and washed with 50 mL ethanol. Thecollected solid was boiled in 200 mL methanol and allowed to cool. Theprecipitate was collected by suction filtration and washed with 75 mLmethanol. The orange solid was dried under high vacuum for 48 hours,giving 136.18 grams 6,6-diphenylfulvene (86.2%).

[0133] 2,5-dichloro-2,5-dimethylhexane. A 2 liter round bottom flask wascharged with 2,5-dimethyl-2,5-hexanediol (200.0 grams, 1.368 mol).Concentrated aqueous HCl (1.00 liter, 12.2 mol HCl) was poured in. Thethick paste was stirred and shaken intermittently for 15 hours. Thesolid was collected by suction filtration and rinsed with 500 mL water.The solid was dissolved in 1100 mL diethyl ether and the residual waterlayer removed. The organic layer was dried over MgSO₄ and pushed througha column of alumina, followed by rinsing the column with 200 mL diethylether. Solvent was removed by rotary distillation to give 235.70 gramsof 2,5-dichloro-2,5-dimethylhexane as white crystals (94.1%).octamethyloctahydrodibenzofluorene. An argon-purged 2 liter vessel wascharged with fluorene (45.30 grams, 0.2725 mol),2,5-dichloro-2,5-dimethylhexane (100.00 grams, 0.5461 mol) andnitromethane (800 mL). The solids were dissolved by gentle heating. Asolution of AlCl₃ (44.65 grams, 0.335 mol) in 60 mL nitromethane wassyringed in over 6 minutes. During the addition, much HCl is evolvedthrough an oil bubbler and precipitate is rapidly formed. After stirringfor 18 hours, the steel blue reaction is filtered and the solidcollected on filter paper. 300 mL water is slowly added to the filtrateand the formed precipitate is collected by suction filtration. Thecombined precipitates were added slowly to 400 mL water. 200 mL hexaneswere added to this and the slurry stirred over night to quench thealuminum chloride. The water layer was removed and the solvent removedfrom the remaining slurry by rotary evaporation. The solid was extractedover a period of 3 days with 300 mL diethyl ether from a celluloseextraction thimble. Diethyl ether was removed by rotary evaporation andthe remaining solid boiled in 100 mL hexanes, cooled, filtered andwashed with 50 mL hexanes. In vacuo drying afforded 87.75 grams ofoctamethyloctahydrodibenzofluorene as a white powder (83.3%).

[0134] (methyl)₂C(9-octamethyloctahydrodibenzofluorenyl)(cyclopentadienyl)H₂. Octamethyloctahydrodibenzofluorene (9.625 g, 24.89mmol) was massed into a 250 mL round bottom schlenk flask. This wasevacuated, backfilled with argon, and charged with 100 mLtetrahydrofuran via syringe. A solution of n-butyllithium in hexanes(16.0 mL, 1.6 M, 25.6 mmol) was syringed in over 10 minutes, givinginitially a red solution, which later formed some red precipitate. After100 minutes, 6,6-dimethylfulvene (3.0 mL, 2.64 g, 24.9 mmol) wassyringed in, yielding a homogenous solution. After 22 hours, 60 mL ofaqueous NH₄Cl were slowly syringed in and the organic layer wasisolated. The aqueous layer was extracted with diethyl ether (2×25 mL)and the combined organic layers were dried over MgSO₄, filtered, androtavapped to give the product as a yellow crystalline solid, 12.27 g intheoretical yield.

[0135] (methyl)₂C(9-octamethyloctahydrodibenzofluorenyl)(cyclopentadienyl)Li₂. A 250 mL round bottom flask was charged with(methyl)₂C(9-octamethyloctahydrodibenzofluorenyl)(cyclopentadienyl)H₂(12.27 grams, 24.89 mmol) and attached to a swivel frit before 75 mL ofdiethyl ether were condensed in. A solution of n-butyllithium in hexanes(32.0 mL, 1.6 M, 51.2 mmol) was syringed in over 3 minutes at 0° C.After stirring for 17 hours at room temperature, solvent was removed and75 mL benzene were condensed in. The solution was frozen and lyophilizedto give 11.80 grams of the dilithio salt as an orange powder (93.9%).

[0136](methyl)₂C(9-octamethyloctahydrodibenzofluoreny!)(cyclopentadienyl)ZrCl2(91). In the glove box, a swivel frit apparatus was charged with(methyl)₂C(9-octamethyloctahydrodibenzofluorenyl)(cyclopentadienyl)Li₂(3.246 g, 6.436 mmol) and zirconium tetrachloride (1.500 g, 6.437 mmol).50 mL of petroleum ether were condensed in and the reaction stirred atroom temperature for 51 hours before solvent removal. 20 mLdichloromethane were condensed in, stirred, and removed. Then, 30 mLdiethyl ether were condensed in, stirred, and removed. In the glove box,the solid was transferred to a cellulose extraction thimble and this wasextracted overnight with 100 mL diethyl ether. The obtained slurry wastransferred back to the swivel frit and the volume reduced to 30 mL. Theorange precipitate (91) was collected on the frit and dried in vacuo:1.649 g (39.2%).

Example 12

[0137] Synthesis of 92

[0138] (phenyl)₂C(9-octamethyloctahydrodibenzofluorenyl)(cyclopentadienyl)H₂. A 300 mL round bottom flask was charged with OctH(12.00 grams, 0.03104 mol) and equipped with a 180° needle valve. Thiswas evacuated and backfilled with argon before 120 mL diethyl ether wereadded via syringe. This was cooled to 0° C. and 21.0 mL ofn-butyllithium in hexanes (1.6 M, 0.0336 mol) were syringed in over 3minutes. The cold bath was removed and the yellow slurry was stirred for21 hours, when solvent was removed by vacuum transfer. In the dry box,6,6-diphenylfulvene (7.148 grams, 0.03104 mol) was added. 150 mL ofdiethyl ether were added by vacuum transfer at −78° C. The cold bath wassubsequently removed and the reaction stirred for 5 days, producing muchtan precipitate. 60 mL of aqueous NH₄Cl were syringed in slowly at 0° C.100 mL water were added and the organic layer was isolated. The waterlayer was extracted with diethyl ether (4×100 mL). The combined organiclayers were dried over MgSO₄ and filtered. Rotary evaporation of thesolvent gave crude product in quantitative yield (19.15 grams). Large,colorless crystals are obtained by recrystallization from boilingethanol.

[0139] (phenyl)₂C(9-octamethyloctahydrodibenzofluorenyl)(cyclopentadienyl) ZrCl₂ (92). A 250 mL round bottom flask was chargedwith(phenyl)₂C(9-octamethyloctahydrodibenzofluorenyl)(cyclopentadienyl)H₂(10.00 grams, 0.01621 mol), equipped with a 180° needle valve andevacuated. In the dry box, LiCH₂Si(CH₃)₃ (3.053 grams, 0.03242 mol) wasadded. 75 mL of diethyl ether and then 25 mL of tetrahydrofuran werecondensed in at −78°. The cold bath was subsequently removed. After 41hours, solvent was removed from the stirred, red solution. In the drybox, ZrCl₄ (3.78 grams, 0.0162 mol) were added. 75 mL of petroleum etherwere condensed in at −78° C. and the cold bath removed. After stirringfor 47 hours, solvent was removed from the orange slurry. Then, 50 mLCH₂Cl₂ were put on/off to quench any unreacted organolithium compounds.Then, 50 mL diethyl ether were put on/off, affording an orange powderwhich was extracted from a cellulose extraction thimble with 200 mLdiethyl ether for 2 days. The volume of the filtrate was condensed to100 mL and the orange precipitate collected on a frit and dried invacuo: 5.028 grams of product (2) is obtained in the first crop. Furtherextraction of the thimble yields another 0.491 grams of product (43.8%total).

EXAMPLES 13-16

[0140] Examples of Metallocene Synthesis for Isotactic Polymerization

Example 13

[0141] Synthesis of 71

[0142] adamantylfulvene. 2-adamantanone (40.22 μg, 267.7 mmol), methanol(200 mL), cyclopentadiene (51.0 mL, 618.9 mmol), and pyrrolidine (20.0mL, 239.6 mmol) were added to a 1 liter round bottom flask. Afterstirring for 70 hours, the yellow precipitate was collected by suctionfiltration and washed with 50 mL methanol. After in vacuo drying, 45.59grams adamantylfulvene were obtained (85.9%).

[0143] 2-methyl-2-adamantylcyclopentadiene. A 500 mL round bottom flaskwas charged with adamantylfulvene (18.00 g, 90.77 mmol) and equippedwith a 180° needle valve. This was evacuated, backfilled with argon andcharged with 120 mL diethyl ether via syringe. At 0° C.,methyllithium/lithium bromide solution (1.5 M in diethyl ether, 225mmol) were syringed in over 10 minutes. Then, 10 mL dimethoxyethane weresyringed in and the reaction was stirred at room temperature for eightdays. The vessel was cooled to 0° C. and 60 mL of aqueous NH₄Cl weresyringed in slowly. The organic layer was isolated and the aqueous layerwas extracted with diethyl ether (3×25 mL). The combined organic layerswere dried over MgSO₄, filtered, and rotavapped to provide the productas a light yellow oil in quantitative yield (19.45 g).

[0144] 3-(2-methyl-2-adamantyl)-6,6-dimethylfulvene. A flask containing19.45 grams (90.74 mmol) of 2-methyl-2-adamantylcyclopentadiene wascharged with 30 mL acetone, 100 mL methanol, and 10 mL pyrrolidine (120mmol). The solution formed a yellow precipitate over 96 hours which wascollected by suction filtration and rinsed with 50 mL methanol. Thematerial was dried in vacuo to provide 20.36 grams of product as ayellow powder (88.2%).

[0145] fluorenyllithium diethyl ether. A 500 mL round bottom flask wascharged with fluorene (47.00 grams, 282.8 mmol) and attached to a largeswivel frit. This was evacuated before 200 mL diethyl ether werecondensed in and 180.0 mL of n-butyllithium solution (1.6 M in hexanes,288 mmol) were syringed in over 20 minutes at room temperature. After 18hours, the yellow precipitate was collected and dried in vacuo toprovide 50.64 grams of the product as a yellow powder (72.7%).

[0146](methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)H₂. Inthe glove box, a 250 mL round bottom flask was charged withfluorenyllithium-diethyl ether (7.744 g, 31.45 mmol) and3-(2-methyl-2-adamantyl)-6,6-dimethylfulvene (8.000 g, 31.45 mmol) andequipped with a 180° needle valve. 75 mL of diethyl ether were condensedin and the reaction was stirred at room temperature for 4 days. 60 mL ofaqueous NH₄Cl were slowly added and the organic layer was isolated. Theaqueous layer was extracted with diethyl ether (2×25 mL) and thecombined organic layers were dried over MgSO₄, filtered, and rotavappedto provide the product as a light yellow oil in quantitative yield(13.23 g).

[0147](methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)Li₂. Aswivel frit containing(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl) (fluorenyl)H₂(13.23 g, 32.45 mmol) was evacuated and charged with 50 mL of diethylether. At 0° C., 42.0 mL of n-butyllithium solution (1.6 M in hexanes,67.2 mmol) were syringed in over 4 minutes. After stirring at roomtemperature for 23 hours, all solvent was removed and 75 mL of petroleumether were condensed in. The red solid was broken up, collected on thefrit, and dried in vacuo to provide the product in quantitative yield(13.60 g).

[0148] (methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71). A 100 mL round bottom flask wascharged with(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)Li₂(4.640 g, 10.73 mmol) and zirconium tetrachloride (2.500 g, 10.73 mmol)and equipped with a 180° needle valve. 40 mL of petroleum ether werecondensed in and the reaction was stirred at room temperature for 70hours. Solvent was removed and the obtained solid was extractedovernight in a soxhlet extractor (cellulose extraction thimble) with 150mL methylene chloride. The filtrate was condensed to 40 mL and theprecipitate was collected and dried in vacuo. 3.246 (52.1%) of 1 wasobtained as an orange powder.

Example 14

[0149] Synthesis of 72

[0150] 2,5-dichloro-2,5-dimethylhexane. A 2 liter round bottom flask wascharged with 2,5-dimethyl-2,5-hexanediol (200.0 grams, 1.368 mol).Concentrated aqueous HCl (1.00 liter, 12.2 mol HCl) was poured in. Thethick paste was stirred and shaken intermittently for 15 hours. Thesolid was collected by suction filtration and rinsed with 500 mL water.The solid was dissolved in 1100 mL diethyl ether and the residual waterlayer removed. The organic layer was dried over MgSO₄ and pushed througha column of alumina, followed by rinsing the column with 200 mL diethylether. Solvent was removed by rotary distillation to give 235.70 gramsof 2,5-dichloro-2,5-dimethylhexane as white crystals (94.1%).

[0151] octamethyloctahydrodibenzofluorene. An argon-purged 2 litervessel was charged with fluorene (45.30 grams, 0.2725 mol),2,5-dichloro-2,5-dimethylhexane (100.00 grams, 0.5461 mol) andnitromethane (800 mL). The solids were dissolved by gentle heating. Asolution of AlCl₃ (44.65 grams, 0.335 mol) in 60 mL nitromethane wassyringed in over 6 minutes. During the addition, much HCl is evolvedthrough an oil bubbler and precipitate is rapidly formed. After stirringfor 18 hours, the steel blue reaction is filtered and the solidcollected on filter paper. 300 mL water is slowly added to the filtrateand the formed precipitate is collected by suction filtration. Thecombined precipitates were added slowly to 400 mL water. 200 mL hexaneswere added to this and the slurry stirred over night to quench thealuminum chloride. The water layer was removed and the solvent removedfrom the remaining slurry by rotary evaporation. The solid was extractedover a period of 3 days with 300 mL diethyl ether from a celluloseextraction thimble. Diethyl ether was removed by rotary evaporation andthe remaining solid boiled in 100 mL hexanes, cooled, filtered andwashed with 50 mL hexanes. In vacuo drying afforded 87.75 grams ofoctamethyloctahydrodibenzofluorene as a white powder (83.3%).

[0152] (methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)H₂. A 250 mL round bottom flask wascharged with octamethyloctahydrodibenzofluorene (6.079 g, 15.72 mmol)and equipped with a 180° needle valve. This was evacuated before 75 mLof diethyl ether were condensed in. 10.5 mL of n-butyllithium solution(1.6 M in hexanes, 16.8 mmol) were syringed into the white slurry atroom temperature over 10 minutes. After 20 hours of stirring at roomtemperature, solvent was removed from the yellow slurry. To this wasadded 3-(2-methyl-2-adamantyl)-6,6-dimethylfulvene (4.000 g, 15.72 mmol)and 75 mL of diethyl ether were condensed in. This reaction was stirredfor 13 days before 60 mL of water were slowly added and the organiclayer was isolated. The aqueous layer was extracted with diethyl ether(2×25 mL) and the combined organic layers were dried over MgSO₄,filtered, and rotavapped to provide the product as a light yellow oil inquantitative yield (10.08 g).

[0153] (methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)Li₂. A swivel frit containing(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)H₂ (10.08 g, 15.72 mmol) wasevacuated and charged with 75 mL of diethyl ether. At room temperature,21.0 mL of n-butyllithium solution (1.6 M in hexanes, 33.6 mmol) weresyringed in over 8 minutes. After stirring at room temperature for 15hours, all solvent was removed and 50 mL petroleum ether were condensedin. An orange precipitate formed slowly and was collected and dried invacuo to provide 3.525 grams of the product as an orange powder (34.2%)

[0154] (methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (72). A swivelfrit apparatus was charged with(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)Li₂(3.525 g, 5.40 mmol) and zirconium tetrachloride (1.258 g, 5.40 mmol).60 mL petroleum ether were condensed in and the reaction stirred at roomtemperature for 20 hours. The reaction was filtered and all solvent wasremoved before the material was lyophilized from 30 mL of benzene. 30 mLof hexamethyldisiloxane were condensed in and the slurry stirred forseveral hours before the red product 2 was collected on the frit anddried in vacuo: 0.614 grams (14.2%).

Examples 15-16

[0155] Synthesis of Catalysts for Syndiotactic Polymerization.

[0156] The following examples describe the syntheses of catalystsdesigned for the polymerization of alpha olefins, and propylene inparticular, with a syndiotactic mictrostructure.

Example 15

[0157] Synthesis of 51

[0158] 3-(2-adamantyl)-6,6-dimethylfulvene. Pyrrolidine (10.0 mL, 0.116mol) was syringed into a solution of 2-adamantanone (25.00 g, 0.1664mol) and cyclopentadiene (30.0 mL, 0.364 mol) in 250 mL of methanol. Thereaction was stirred for 92 hours before the yellow precipitate wascollected by suction filtration, rinsed with a small volume of methanoland dried in vacuo. 25.71 grams (77.9%) of adamantyl fulvene wereisolated. 6.00 grams (0.0303 mol) of this product were dissolved in 30mL of tetrahydrofuran and this solution added over 30 minutes to atstirred slurry of LiAlH₄ (1.40 g, 0.0369 mol) at 0° C. After 5 hours ofstirring at room temperature, the reaction was cooled to 0° C. andquenched by slow addition of 20 mL of saturated NH₄Cl solution. Then 300mL H₂O, 25 mL concentrated HCl, and 50 mL diethyl ether were added, theorganic layer isolated, and the aqueous layer extracted with additiondiethyl ether (3×50 mL). The combined organic layers were dried overMgSO₄, filtered, and rotavapped to give the product,(2-adamantyl)cyclopentadiene, in quantitative yield as a light yellowoil. To this material was added 50 mL methanol, 50 mL ethanol, 20 mLtetrahydrofuran, 36 mL acetone (0.49 mol) and 0.5 mL pyrrolidine (0.006mol). After stirring for 48 hours, 5 mL of acetic acid were injected,followed by 200 mL H₂O and 200 mL diethyl ether. The organic layer wasisolated and the aqueous layer extracted with diethyl ether (3×40 mL).The combined organic layers were extracted with H₂O (3×25 mL) and with10% aqueous NaOH (3×25 mL), dried over MgSO₄, filtered and rotavapped.The obtained yellow solid was further purified by overnight soxletextraction by 150 mL methanol. The precipitate in the filtrate wasisolated by filtration at 0° C., and in vacuo drying: 4.54 g (62.5%) of3-(2-adamantyl)-6,6-dimethylfulvene, as a yellow powder.

[0159] (methyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)ZrCl₂ (51).10.5 mL of an n-butyllithium solution (1.6 M in hexanes, 0.0168 mol) wassyringed into a solution of sublimed fluorene (2.77 g, 0.0166 mol) in 60mL tetrahydrofuran. After stirring for 5 hours, a solution of3-(2-adamantyl)-6,6-dimethylfulvene (4.00 g, 0.0166 mol) in 40 mLtetrahydrofuran was injected over 2 minutes. After stirring for 20hours, 60 mL of a saturated NH₄Cl solution were added, the organic layerisolated, and the aqueous layer extracted with diethyl ether (2×25 mL).The combined organic layers were dried over MgSO₄, filtered androtavapped to give the product(methyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)H₂ in quantitativeyield as a yellow oil. The dianion was prepared by treating a solutionof this oil in 75 mL diethyl ether with 22.0 mL of n-butyllithiumsolution (1.6 M in hexanes, 0.0352 mol) at 0° C. After stirring for 21hours, the solvent was removed by vacuum transfer and 50 mL of petroleumether were condensed in. The dilithio salt,(methyl)₂C(3-(2-adamantyl)cyclopentadienyl) (fluorenyl)Li₂, was isolatedby filtration and in vacuo drying in quantitative yield as an orangepowder. 2.00 grams of the dilithio salt (0.00478 mol) and 1.114 gsublimed ZrCl₄ (0.00478 mol) were combined in a swivel frit apparatus.40 mL of petroleum ether were condensed in at −78° C. This was allowedto warm slowly to room temperature before solvent removal after 14 hoursif stirring. 40 mL of methylene chloride were condensed in and removedin order to quench unreacted ligand. Then the orange solid was extractedin the swivel frit with 50 mL of refluxing diethyl ether. Two crops wereobtained for a total of 1.502 grams (55.5%) of 51 as an orange powderfollowing collection at 0° C. and in vacuo drying.

Example 16

[0160] Synthesis of 52

[0161] adamantylfulvene. 2-adamantanone (40.22 g, 267.7 mmol), methanol(200 mL), cyclopentadiene (51.0 mL, 618.9 mmol), and pyrrolidine (20.0mL, 239.6 mmol) were added to a 1 liter round bottom flask. Afterstirring for 70 hours, the yellow precipitate was collected by suctionfiltration and washed with 50 mL methanol. After in vacuo drying, 45.59grams adamantylfulvene were obtained (85.9%).

[0162] 2-adamantylcyclopentadiene. A 500 mL argon-purged round bottomflask was charged with LiAlH₄ (8.20 g, 216 mmol) and 100 mLtetrahydrofuran. Adamantylfulvene (30.00 g, 151.3 mmol) was added viasolid addition funnel, followed by another 100 mL tetrahydrofuran over 2minutes at 0° C. After stirring for 22 hours at room temperature, thereaction was cooled to 0° C. and 100 mL water were added dropwise over60 minutes. Then, 100 mL concentrated aqueous HCl in 300 mL water and 50mL diethyl ether were added. The organic later was isolated and theaqueous layer extracted with diethyl ether (3×50 mL). The combinedorganic layers were dried over MgSO₄, filtered, and rotavapped to give30.30 g of product in quantitative yield.

[0163] 3-(2-adamantyl)-6,6-diphenylfulvene. A 250 mL round bottom flaskwas charged with 2-adamantylcyclopentadiene (10.24 g, 51.13 mmol),benzophenone (9.32 g, 51.13 mmol) and 100 mL absolute ethanol. Once thesolids had dissolved, sodium methoxide (5.00 g, 92.6 mmol) was added andthe reaction was stirred for five days. The orange precipitate wascollected by suction filtration and washed with 50 mL ethanol. The airdried product was stirred in 100 methanol overnight and the solid wascollected by suction filtration and washed with 50 mL methanol. Dryingin vacuo for several hours provided 13.32 grams of desired product(71.5%).

[0164] (phenyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)H₂. In theglove box, a 250 mL round bottom flask was charged with3-(2-adamantyl)-6,6-diphenylfulvene (6.000 g, 16.46 mmol) andfluorenyllithium diethyl ether adduct (4.054 g, 16.46 mmol). This wasequipped with a 180° needle valve and 100 mL of diethyl ether werecondensed in to the reaction vessel. After stirring at room temperaturefor 7 days, 60 mL of aqueous NH₄Cl and 50 mL water were slowly added.After 2 hours, the solid that formed was collected by filtration andwashed with 40 mL diethyl ether. The crude, wet product was dissolved in250 mL tetrahydrofuran, dried over MgSO₄, filtered, rotavapped, anddried in vacuo to give 2.834 grams of a waxy solid as the product(32.4%).

[0165] (phenyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)ZrCl₂ (52).2.834 grams of (phenyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)H₂(5.340 mmol) was combined with LiCH₂(trimethylsilane) (1.006 g, 10.68mmol) in a 250 mL round bottom flask. 50 mL of tetrahydrofuran werecondensed in and this was stirred at room temperature for 17 hours, whenthe solvent was removed. In the glove box, zirconium tetrachloride(1.245 g, 5.343 mmol) was added. 60 mL of petroleum ether were condensedin and the reaction stirred at room temperature for 52 hours. Solventwas removed and 20 mL of dichloromethane were condensed in, stirred, andremoved. Then, 50 mL of diethyl ether were condensed in, stirred, andremoved. The solid was extracted overnight in a cellulose extractionthimble with 150 mL methylene chloride. The obtained solution wasfiltered through a frit. Solvent was removed, 15 mL of diethyl etherwere condensed in, and the orange solid was broken up, collected at 0°C., and dried in vacuo to give 0.778 grams of product 52 (21.1%).

[0166] II. Polymerization

[0167] Propylene Polymerization Procedures. CAUTION: All polymerizationprocedures should be performed behind a blast shield. All polymerizationreactions were prepared in nitrogen filled gloveboxes. Methylaluminoxane(MAO) was purchased as a toluene solution from Albemarle Corporation andused as the dry powder obtained by in vacuo removal of all volatiles.Toluene was dried over sodium and distilled. Propylene from ScottSpecialty Gases (>99.5%) was used following drying through a Matheson6110 drying system equipped with an OXYSORB™ column. Polymerizationswere conducted in Lab Crest glass reaction vessels (12 oz. for propylenevolumes greater than 60 mL, or 3 oz. for propylene volumes less than 60mL) and were stirred with a magnetic stir bar. Monomer was condensedinto the vessel over several minutes at 0° C. The vessel was thenequilibrated at either 0° C. or at 20° C. with an ice or water bath for10 minutes. A given reaction commenced upon injection of a toluenesolution of the metallocene into the vessel with a 2.5 mL Hamiltonsyringe rated to 200 psi. Temperature maintenance was monitored by anaffixed pressure gauge. Polymerization reactions were vented andquenched with a small volume of methanol/concentrated HCl (12: 1) andthe polymers were separated from hydrolyzed aluminoxanes byprecipitation from methanol. Toluene and methanol were removed from theobtained polymers by in vacuo drying.

Examples 17-25

[0168] Isotactic Polymerizations

[0169] These examples illustrate the polymerization of propylene undersuitable conditions and with suitable catalysts for the production ofisotactic polypropylene.

Example 17

[0170] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.100 g, 1.72×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71), (0.001 g, 1.7×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 0° C. ice/water bath for 10minutes. The reaction was vented and quenched with dilute HCl/methanol.0.410 grams of solid polypropylene were obtained. The polymer has amelting temperature of 157.6° C.

Example 18

[0171] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.100 g, 1.72×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71), (0.001 g, 1.7×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 20° C. water bath for 10minutes. The reaction was vented and quenched with dilute HCl/methanol.0.825 grams of solid polypropylene were obtained. The polymer has amelting temperature of 154.0° C.

Example 19

[0172] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.200 g, 3.44×10⁻³ mol [Al]). Propylene (60 mL) was condensed in at 0°C. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71), (0.002 g, 3.4×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 0° C. ice/water bath for 60minutes. The reaction was vented and quenched with dilute HCl/methanol.3.879 grams of solid polypropylene were obtained. The polymer has amelting temperature of 159.7° C.

Example 20

[0173] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.200 g, 3.44×10⁻³ mol [Al]). Propylene (55 mL) was condensed in at 0°C. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71), (0.002 g, 3.4×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 0° C. ice/water bath for 10minutes. The reaction was vented and quenched with dilute HCl/methanol.1.375 grams of solid polypropylene were obtained. The polymer has amelting temperature of 159.1° C.

Example 21

[0174] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.200 g, 3.44×10⁻³ mol [Al]). Propylene (55 mL) was condensed in at 0°C. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71), (0.002 g, 3.4×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 20° C. water bath for 10minutes. The reaction was vented and quenched with dilute HCl/methanol.2.133 grams of solid polypropylene were obtained. The polymer has amelting temperature of 156.3° C.

Example 22

[0175] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.200 g, 3.44×10⁻³ mol [Al]) and 28.0 mL toluene. Propylene (3 mL) wascondensed in. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71), (0.002 g, 3.4×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 0° C. ice/water bath for 180minutes. The reaction was vented and quenched with dilute HCl/methanol.0.869 grams of solid polypropylene were obtained. The polymer has amelting temperature of 157.6° C.

Example 23

[0176] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.200 g, 3.44×10⁻³ mol [Al]) and 28.0 mL toluene. Propylene (3 mL) wascondensed in. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(fluorenyl)zirconium dichloride (71), (0.002 g, 3.4×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 20° C. water bath for 90minutes. The reaction was vented and quenched with dilute HCl/methanol.0.503 grams of solid polypropylene were obtained. The polymer has amelting temperature of 147.7° C.

Example 24

[0177] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.145 g, 2.50×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (72), (0.002 g, 2.5×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 0° C. ice/water bath for 20minutes. The reaction was vented and quenched with dilute HCl/methanol.0.293 grams of solid polypropylene were obtained. The polymer has amelting temperature of 167.0° C.

Example 25

[0178] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.145 g, 2.50×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of(methyl)₂C(3-(2-methyl-2-adamantyl)cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (72), (0.002 g, 2.5×10⁻⁶ mol) in toluene (2.0 mL)was injected and the reaction stirred in a 20° C. water bath for 20minutes. The reaction was vented and quenched with dilute HCl/methanol.0.704 grams of solid polypropylene were obtained. The polymer has amelting temperature of 162.7° C.

Examples 26-30

[0179] Syndiotactic Polymerizations

[0180] Examples of propylene polymerization with theR₂C(Cp¹)(Oct¹)zirconium dichloride/methylaluminoxane catalyst system.

Example 26

[0181] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.444 g, 7.65×10⁻³ mol [Al]). Propylene (25 mL) was condensed in at 0°C. A solution of (methyl)₂C(Cp)(Oct)ZrCl₂ (91, 0.010 g, 1.5×10⁻⁵ mol) intoluene (2.0 mL) was injected and the reaction stirred in a 0° C.ice/water bath for 8 minutes. The reaction was vented and quenched withdilute HCl/methanol. 8.68 grams of solid polypropylene were obtained.The polymer has a melting temperature of 153° C.

Example 27

[0182] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.089 g, 1.53×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of (methyl)₂C(Cp)(Oct)ZrCl₂ (91, 0.0005 g, 7.7×10⁻⁷ mol)in toluene (1.0 mL) was injected and the reaction stirred in a 0° C.ice/water bath for 10 minutes. The reaction was vented and quenched withdilute HCl/methanol. 0.264 grams of solid polypropylene were obtained.

Example 28

[0183] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.089 g, 1.53×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of (methyl)₂C(Cp)(Oct)ZrCl₂ (91, 0.0005 g, 7.7×₁₀-7 mol)in toluene (1.0 mL) was injected and the reaction stirred in a 20° C.water bath for 10 minutes. The reaction was vented and quenched withdilute HCl/methanol. 0.261 grams of solid polypropylene were obtained.

Example 29

[0184] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.075 g, 1.3×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of (phenyl)₂C(Cp)(Oct)ZrCl₂ (92, 0.0005 g, 6×10⁻⁷ mol) intoluene (1.0 mL) was injected and the reaction stirred in a 0° C.ice/water bath for 10 minutes. The reaction was vented and quenched withdilute HCl/methanol. 0.475 grams of solid polypropylene were obtained.The polymer has a melting temperature of 153° C.

Example 30

[0185] A 100 mL Lab Crest glass pressure reactor was charged with MAO(0.075 g, 1.3×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0°C. A solution of (phenyl)₂C(Cp)(Oct)ZrCl₂ (92, 0.0005 g, 6×10⁻⁷ mol) intoluene (1.0 mL) was injected and the reaction stirred in a 20° C. waterbath for 10 minutes. The reaction was vented and quenched with diluteHCl/methanol. 1.160 grams of solid polypropylene were obtained. Thepolymer has a melting temperature of 152° C.

Examples 31-44

[0186] Polymerization of Elastomeric Polyolefins

[0187] Examples 31-44 demonstrate the polymerization of polypropylene bya number of catalysts of the invention.

Example 31

[0188] A 100 mL Lab Crest pressure reactor was charged with MAO (0.256g, 4.41×10⁻³ mol [Al]). Propylene (25 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)ZrCl₂(111, 0.005 g, 9×10⁻⁶ mol) in toluene (1.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 30 minutes. The reactionwas vented and quenched with methanol. 5.97 grams of elastomericpolypropylene were obtained.

Example 32

[0189] A 200 mL Lab Crest pressure reactor was charged with MAO (0.205g, 3.53×10⁻³ mol [Al]). Propylene (100 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)ZrCl₂(111, 0.001 g, 1.8×10⁻⁶ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 120 minutes. The reactionwas vented and quenched with methanol. 15.03 grams of elastomericpolypropylene were obtained.

Example 33

[0190] A 200 mL Lab Crest pressure reactor was charged with MAO (0.205g, 3.53×10⁻³ mol [Al]). Propylene (100 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)ZrCl₂(111, 0.001 g, 1.8×10⁻⁶ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 20° C. water bath for 90 minutes. The reaction wasvented and quenched with methanol. 20.98 grams of elastomericpolypropylene were obtained.

Example 34

[0191] A 100 mL Lab Crest pressure reactor was charged with MAO (0.444g, 7.65×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)HfCl₂(112, 0.005 g, 7.6×10⁻⁶ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 60 minutes. The reactionwas vented and quenched with methanol. 0.151 grams of elastomericpolypropylene were obtained.

Example 35

[0192] A 100 mL Lab Crest pressure reactor was charged with MAO (0.444g, 7.65×10⁻³ mol [Al]). Propylene (30 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)HfCl₂(112, 0.005 g, 7.6×10⁻⁶ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 20° C. water bath for 60 minutes. The reaction wasvented and quenched with methanol. 2.34 grams of elastomericpolypropylene were obtained.

Example 36

[0193] A 100 mL Lab Crest pressure reactor was charged with MAO (0.508g, 8.76×10⁻³ mol [Al]). Propylene (25 mL) was condensed in at 0° C. Asolution of(methyl)₂C(3-(3,3,5,5-tetramethylcyclohexyl)cyclopentadienyl)(fluorenyl)ZrCl₂(113, 0.010 g, 1.8×10⁻⁵ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 25 minutes. The reactionwas vented and quenched with methanol. 11.11 grams of firm, yet rubberypolypropylene were obtained.

Example 37

[0194] A 100 mL Lab Crest pressure reactor was charged with MAO (0.282g, 4.86×10⁻³ mol [Al]). Propylene (25 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-cyclohexylcyclopentadienyl)(fluorenyl)ZrCl2(114, 0.005 g, 1×10⁻⁵ mol) in toluene (1.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 5 minutes. The reactionwas vented and quenched with methanol. 6.23 grams of rubberypolypropylene were obtained.

Example 38

[0195] A 100 mL Lab Crest pressure reactor was charged with MAO (0.577g, 9.95×10⁻³ mol [Al]). Propylene (20 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-neopentylcyclopentadienyl)(fluorenyl)ZrCl2(115, 0.010 g, 2.0×10⁻⁵ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 5 minutes. The reactionwas vented and quenched with methanol. 6.21 grams of rubberypolypropylene were obtained.

Example 39

[0196] A 100 mL Lab Crest pressure reactor was charged with MAO (0.100g, 1.72×10⁻³ mol [Al]). Propylene (25 mL) was condensed in at 0° C. Asolution of (methyl)₂C(3-neopentylcyclopentadienyl)(fluorenyl)ZrCl₂(115, 0.001 g, 2×10⁻⁶ mol) in toluene (1.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 10 minutes. The reactionwas vented and quenched with methanol. 4.01 grams of rubberypolypropylene were obtained.

Example 40

[0197] A 100 mL Lab Crest pressure reactor was charged with MAO (0.508g, 8.76×10⁻³ mol [Al]). Propylene (25 mL) was condensed in at 0° C. Asolution of(methyl)₂C(3-(4-tert-butylcyclohexyl)cyclopentadienyl)(fluorenyl)ZrCl₂(116, 0.010 g, 1.8×10⁻⁵ mol) in toluene (1.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 5 minutes. The reactionwas vented and quenched with methanol. 7.57 grams of rubberypolypropylene were obtained.

Example 41

[0198] A 100 mL Lab Crest pressure reactor was charged with MAO (0.561g, 9.67×10⁻³ mol [Al]). Propylene (25 mL) was condensed in at 0° C. Asolution of(methyl)₂C(3-(3,3-dimethyl-2-butyl)cyclopentadienyl)(fluorenyl)ZrCl₂(117, 0.010 g, 2.0×10⁻⁵ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 6 minutes. The reactionwas vented and quenched with methanol. 7.86 grams of somewhat rigid,rubbery polypropylene were obtained.

Example 42

[0199] A 400 mL Lab Crest pressure reactor was charged with MAO (1.260g, 21.7 mmol [Al]). Propylene (350 mL) was condensed in at 0° C. Asolution of (phenyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)ZrCl₂(118, 0.015 g, 2.2×10⁻⁵ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 0° C. ice/water bath for 90 minutes. The reactionwas vented and quenched with methanol. 23.22 grams of elastomericpolypropylene were obtained. Properties of this polymer, SM-IV-100, arelisted below.

Example 43

[0200] A 400 mL Lab Crest pressure reactor was charged with MAO (1.260g, 21.7 mmol [Al]). Propylene (350 mL) was condensed in at 0° C. Asolution of (phenyl)₂C(3-(2-adamantyl)cyclopentadienyl)(fluorenyl)ZrCl₂(118, 0.015 g, 2.2×10⁻⁵ mol) in toluene (2.0 mL) was injected and thereaction stirred in a 20° C. water bath for 30 minutes. The reaction wasvented and quenched with methanol. 27.76 grams of elastomericpolypropylene were obtained. Properties of this polymer, SM-IV-101, arelisted in Table XYZ.

EXAMPLE 44

[0201] TABLE 1 Polymerization data with 1-9/MAO in liquid propylene.Activity Metallocene MAO T_(p) Tol. C₃H₆ Time Yield gP T_(m) ^(a) m mmmmEntry (mg) (equiv.) (° C.) (mL) (mL) (min.) (g) {overscore (gmet h)} (°C.) (%) (%) M_(w) M_(w)/M_(n) 1 1 (1.0) 1000 0 2.0 30 15 1.43 5710 n.o.50.4 21.6 80,000 1.81 2 1 (1.0) 1000 20 2.0 30 10 4.95 29700 n.o. 49.618.3 3 2 (0.5) 2000 0 1.0 30 30 1.50 6020 n.o. 62.3 28.4 134,000 3.15 42 (0.5) 2000 20 1.0 30 10 1.08 12900 88 62.7 31.4 81,900 4.38 5 2 (2.0)1000 0 2.0 55 60 9.96 5000 n.o. 61.0 28.0 6 3 (5.0) 1000 0 2.0 30 600.15 30 n.o 64.4 32.0 7 3 (5.0) 1000 20 2.0 30 60 2.34 470 n.o. 66.434.0 8 4 (15) 1000 0 2.0 350 90 23.22 1030 115 57.8 27.2 638,000 2.33 94 (15) 1000 20 2.0 350 30 27.76 3700 125 55.7 25.3 435,000 2.14 10 4(2.0) 1000 0 2.0 180 180 11.27 1900 147 57.9 25.9 1,081,000 2.33 11 4(6.0) 1000 0 2.0 200 70 26.02 3700 146 58.7 26.6 1,006,000 2.42 12 4(2.0) 1000 0 2.0 200 360 13.85 1200 125 58.8 27.7 802,000 2.43 13 5(5.0) 1000 0 2.0 55 60 0.19 38 134 58.8 26.6 14 5 (5.0) 1000 20 2.0 5560 1.92 384 n.o. 58.8 28.1 15 5 (15) 1000 20 2.0 55 60 8.03 540 135 57.624.0 806,000 1.93 16 6 (1.0) 1000 0 2.0 30 15 1.31 5220 122 57.6 27.5105,000 1.93 17 6 (1.0) 1000 20 2.0 30 10 3.74 22500 n.o. 58.4 28.0 18 7(2.0) 1000 0 2.0 55 60 8.38 4190 148 43.8 14.7 572,000 2.55 19 7 (2.0)1000 20 2.0 55 30 12.50 12500 147 50.6 18.5 390,000 2.32 20 8 (2.0) 10000 2.0 30 30 1.57 1570 98 75.3 49.3 77,400 2.01 21 8 (2.0) 1000 20 2.0 3015 3.54 7070 91 75.0 47.9 22 9 (1.0) 1000 0 2.0 30 3 1.23 24600 n.o.57.5 26.9 653,000 1.87 23 9 (0.5) 1000 20 1.0 30 3 1.12 44700 n.o. 61.030.0 397,000 2.31 24 9 (1.0) 1000 20 2.0 55 15 10.22 41000 149 63.0 31.8535,000 2.21

[0202] III. Polymer Properties

[0203] Polymer Characterization. Polymer melting temperatures weredetermined by differential scanning calorimetry (Perkin-Elmer DSC 7).Typically four or five scans (from 50 to 200° C. at 10° C./minute) wererequired to find similar melting temperatures among the last two orthree scans. Certain melting temperatures (Entries in Table 2: 8-12, 15,18, 19 and 24) were determined by BP-Amoco with scan rate of 20°C./minute. Polymer molecular weights were determined by BP-Amoco and byExxon.

[0204] Mechanical properties were determined using standard protocolsand the test specimens were compression molded according to ASTM D1708.For mechanical testing, the crosshead separation rate was 50.8 cm./min.Exxon used the following protocol:

[0205] Plaques suitable for physical property testing were compressionmolded on a Carver hydraulic press. 6.5 g of polymer was molded betweenbrass plates (0.05″ thick) lined with Teflon coated aluminum foil. A0.033″ thick chase with a square opening 4″×4″ was used to controlsample thickness. After one minute of preheat at 120, under minimalpressure, the hydraulic load was gradually increased to ˜10,000-15,000lbs. at which it was held for three minutes. Subsequently the sample andmolding plates were cooled for three minutes under ˜10,000 to 15,000lbs. load between the water cooled platens of the press. Plaques wereallowed to equilibrate at room temperature for a minimum of one weekprior to physical property testing. Dogbones for tensile testing werecut from compression molded plaques using a mallet handle die. Specimendimensions were those specified in ASTM D 1708. Tensile properties weremeasured on an Instron model 4502 equipped with a 22.48 lb. load celland pneumatic jaws fitted with serrated grip faces. Five specimens ofeach sample were tested. Deformation was performed at a constantcrosshead speed of 5.0 in./min. with a data sampling rate of 25points/second. Jaw separation prior to testing was 0.876″, from whichstrains were calculated assuming affine deformation. Initial modulus,stress and strain at yield (where evident), stress at 100%, 200%, 300%,400%, 500% and 1,000% strain, and stress and strain at break werecalculated. A minimum of five specimens from each plaque were tested,the results being reported as the average value. All stresses quoted are“engineering” values, i.e., they are calculated based upon the originalcross-sectional area of the specimen, taking no account of reducedcross-section as a function of increasing strain. Strain values inexcess of 500% are questionable; most samples pulled out of the grips tosome extent at higher strains. Thus, the strain calculated fromcrosshead separation is larger than the strain experienced in the gaugeregion of the sample. This phenomenon was particularly apparent insamples that exhibited high degrees of strain hardening. Elasticrecovery experiments were performed on the Instron 4502 tensile testerusing samples with the same specimen dimensions as those used in tensileexperiments. Three specimens of each sample were tested. Prior totesting a pair of fiducial ink marks were placed on the gauge region ofthe sample 0.5″ apart (with an Ultra Fine Point Sharpie marker pen). Thesample was extended to a nominal 200% elongation (crosshead displacement1.752″) at a crosshead speed of 20 in./min. Once it reached thisextension, the crosshead travel was automatically reversed and thecrosshead returned to its original position at 20 in./min. The samplewas immediately removed from the grips and the separation of the inkmarks was measured with calipers. Recovery from the fiducial marks iscalculated according to: Recovery from 200% strain (%)=100(E−0.5)/(0.5), where E=Fiducial mark separation after 24 hours. Results:All samples drew affinely. No samples exhibited a yield peak. Allsamples strain whitened to some extent. This was particularly noticeablein the sample from Entry 15, in which the whitening was irreversible.

Example 45

[0206] TABLE 2 Thermal and mechanical properties of elastomericpolypropylenes. Entry 5 8 9 10 11 Thermal Properties melt flow rate(g/600 s, 230° C.) 0.1 0.41 T_(g) (° C.) −3 −3 T_(m) (° C.) n.o. 115 125147 146 H_(m) (J/g) 9.3 6.8 5.4 4.5 T_(c) (° C.) 66 62 88 86 H_(c) (J/g)4.6 2.7 8.7 3.1 Mechanical Properties initial modulus (psi) 1007 ± 44679 712 stress at 100% strain (psi)  226 ± 2  stress at 200% strain(psi)  249 ± 3  stress at 300% strain (psi)  180 ± 2  stress at 400%strain (psi)  325 ± 3  stress at 500% strain (psi)  379 ± 2  stress at1000% strain (psi)  895 ± 10 stress at break (psi) 1233 ± 27 1215 1230strain at break (%) 1245 ± 30 756 813 % recovery, trial 1 11.3 %recovery, trial 2 7.60 % recovery, trial 3 9.10 % recovery, average^(a)9.33 tensile stress relaxation (%)^(b) 27 28 tensile hysteresis:^(c)cumulative set (%)^(d) 6.5 7.3 retained force (%)^(e) 51 49 [m] (%) 61.057.8 55.7 57.9 58.7 M_(n) 43,000^(f) 273,000 204,000 463,000 416,000

Example 46

[0207] TABLE 3 Thermal and mechanical properties of elastomericpolypropylenes. Entry 12 15 18 19 24 Thermal Properties melt flow rate(g/600 s, 230° C.) T_(g) (° C.) T_(m) (° C.) 125 135 148 147 149 H_(m)(J/g) 0.5 0.7 6.6 6.5 2.2 T_(c) (° C.) 78 87 82 79 H_(c) (J/g) 1.9 7.17.8 3.6 Mechanical Properties initial modulus (psi) 509 ± 23  483 ± 23 1100 ± 33  stress at 100% strain (psi) 222 ± 24  155 ± 1  260 ± 4 stress at 200% strain (psi) 313 ± 7  170 ± 1  305 ± 3  stress at 300%strain (psi) 415 ± 9  174 ± 1  366 ± 3  stress at 400% strain (psi) 530± 12  181 ± 1  459 ± 6  stress at 500% strain (psi) 660 ± 14  191 ± 1 586 ± 9  stress at 1000% strain (psi) NA 328 ± 8  NA stress at break(psi) 1219 ± 70  642 ± 43  1763 ± 299  strain at break (%) 792 ± 32 1447 ± 45  910 ± 75  % recovery, trial 1 0.70 3.70 3.60 % recovery,trial 2 2.10 5.70 3.40 % recovery, trial 3 1.8 5.00 4.9 % recovery,average^(a) 1.53 4.80 3.97 tensile stress relaxation (%)^(b) tensilehysteresis:^(c) cumulative set (%)^(d) retained force (%)^(e) [m] (%)58.8 57.6 43.8 50.6 63.0 M_(n) 330,000 417,000 224,000 168,000 242,000

Example 47

[0208] TABLE 4 Thermal and mechanical properties of elastomericpolypropylenes. SM-IV-100 SM-IV-101 melt flow rate, 230° C. g/10 min 0.10.41 mmmm, % 27 27 thermal properties T_(g), ° C. −3 −2.9 T_(m), ° C.115 125 H_(m), J/g 9.3 6.8 T_(c), ° C. 66 62 H_(c), J/g 4.6 2.7 tensileproperties modulus, MPa 4.68 4.84 elongation to break, % 756 813strength at break, MPa 8.38 8.48 tensile stress relaxation, 50%elongation 27 28 stress decay, %, 5 minutes tensile hysteresis, 3cycles, 100% elongation 30 second hold at extension, 60 second hold atrecovery: cumulative % set, 2 cycles 6.5 7.3 retained force, %, 2ndcycle 51 49 (stress at 50% on recovery/stress at 100% on extensionbefore hold)

Example 48

[0209]¹³C NMR Determination of Polyolefin Tacticity

[0210] This example shows that the elastomeric polypropylenes of theinvention are predominantly hemiisotactic isotactic stereocopolymers.Hemiisotactic PP generally is missing the mmrm+rrmr and mrmr pentads. Inour case, these pentads make up just a small percentage of the polymer,consistent with the general hemiisotactic regime. TABLE 5 13C NMRderived pentad analysis. (mmrm and rrmr overlap in the NMR spectra andare grouped for anaylsis). Entry 1 2 3 4 5 6 7 8 mmmm 21.6 18.3 28.431.4 28.0 32.0 34.0 27.2 mmmr 10.9 11.6 15.5 14.7 14.3 15.3 15.3 13.2rmmr 6.0 5.5 5.3 4.5 5.7 4.6 5.1 5.5 mmrr 21.8 22.5 24.7 23.1 24.6 23.521.5 22.2 mmrm + rrmr 1.3 1.9 0.8 0.9 1.1 1.2 1.4 1.2 mrmr 0.6 0.8 0.40.4 0.5 0.4 0.9 0.6 rrrr 23.1 21.3 7.9 8.2 8.1 7.5 6.6 12.5 rrrm 10.311.7 7.4 8.5 8.9 6.9 7.0 9.1 mrrm 4.4 6.5 9.5 8.4 9.0 8.7 8.0 8.5 Entry9 10 11 12 13 14 15 16 mmmm 25.3 25.9 26.6 27.7 26.6 28.1 24.0 27.5 mmmr13.2 13.6 13.9 13.4 13.2 13.5 14.9 12.9 rmmr 5.0 5.8 5.5 5.2 6.3 5.0 6.15.1 mmrr 21.5 23.4 23.5 22.6 23.1 22.3 24.0 21.3 mmrm + rrmr 2.3 1.2 1.31.4 1.3 1.6 1.0 2.0 mrmr 0.6 0.6 0.7 0.8 0.7 0.5 0.2 1.1 rrrr 11.6 12.211.4 12.3 12.7 11.1 11.8 13.6 rrrm 11.1 9.4 9.4 9.0 8.9 10.2 9.4 8.8mrrm 9.3 7.8 7.8 7.5 7.2 7.7 8.5 7.8 Entry 17 18 19 20 21 22 23 24 mmmm28.0 14.7 18.5 49.3 47.9 26.9 30.0 31.8 mmmr 13.3 9.8 13.4 13.2 14.313.4 15.1 15.3 rmmr 4.8 6.1 6.7 3.2 2.8 4.8 3.1 3.0 mmrr 21.7 22.7 21.615.5 16.8 20.4 19.2 19.3 mmrm + rrmr 2.2 2.9 1.6 2.6 2.0 4.2 5.2 5.4mrmr 1.0 0.6 0.8 1.0 1.2 0.2 1.2 1.4 rrrr 12.3 21.1 20.4 3.5 4.0 11.78.9 8.0 rrrm 9.4 13.4 10.6 4.3 4.1 10.8 8.7 7.8 mrrm 7.3 8.6 6.5 7.3 6.97.6 8.6 8.1

Example 49

[0211] Derivation of Isotactic Block Length Distribution forIsotactic-Hemiisotactic Polypropylene

[0212] This example describes a statistical model of polymer tacticity.One can calculate the isotactic block length distribution forisotactic-hemiisotactic polypropylene. For a hemiisotactic regime, onlysequential rr and mm triads are allowed. Therefore, only isotacticblocks containing an odd number of monomers will be allowed and anisotactic block will be defined by (rr)(mm)(s)(rr), where s is thenumber of repeating mm triads.¹⁶ The probability of creating anisotactic block of length n will be given byP_(n)=(1−α)(α)^(((n−1)/2))(1−α), and the number of blocks with length nin a given polymer chain is N_(n)=P_(n)(P_(d)), where P_(d) is thedegree of polymerization.¹⁷

[0213] For a polymer with a=0.62 and M_(n)=100,000, this analysispredicts that the longest isotactic segment present (N_(n)=1) willcontain 25 monomer units and there will be a total of 7 blocks of 21monomer units or longer. Doubling the molecular weight (M_(n)=200,000)results in a polymer for which the longest isotactic segment is 27monomer units long, but for which there are 15 blocks of 21 monomerunits or longer.

[0214] For a polymer with a=0.50, the longest isotactic segments presentwill contain only 19 or 21 monomer units, for M_(n)=100,000 orM_(n)=200,000, respectively. Such a polymer does not contain isotacticblocks in great enough number or length to form the crystalline regionsnecessary for elastomeric polypropylene.

[0215] Finally, for a polymer with a=0.75, the longest isotacticsegments present will contain 35 or 39 monomer units and there will be33 or 67 blocks of length 21 or greater, for M_(n)=100,000 orM_(n)=200,000, respectively. Clearly these will be present at theexpense of the requisite amorphous hemiisotactic segments and a rigidpolymer will result.

Example 50

[0216] Derivation of the Isotactic Block Length Distribution forIsotactic-Hemiisotactic Polypropylene

[0217] This example shows the derivation for g=0 of block length inelastomeric polypropylene polymers. For a hemiisotactic regime, everyother stereocenter is of the same stereochemistry and the interveningstereocenters are of variable stereochemistry. Therefore, as in thehemiisotactic polymer shown below, a given polymer can be represented bya string of mm and rr triads. This disallows the pentads containingisolated m and r dyads: mmrm, rrmr and mrmr. For a given triad, if theprobability of obtaining an mm triad is defined as a, then theprobability of obtaining an rr triad is 1−α.

[0218] An isotactic block is defined as a collection of m dyadsterminated on either end by an r dyad. Since only (mm) and (rr) triadsare allowed for hemisotactic polypropylene, an isotactic block must be acollection of (mm) triads terminated on either end by (rr) triads:(rr)(mm)^((s))(rr), where s is the number of repeating (mm) triads. Theprobability of such a sequence will be the product of the individualprobabilities.

[0219] For example, the isotactic block drawn below containing 13monomer units is described by (rr)(mm)⁽⁶⁾(rr) and the probability offorming it will be P₁₃=(1−α)(α)^((s))(1−a), where s=6. Since thevariables s and n are related as s=((n−1)/2), we can generalize for theprobability of obtaining an isotactic block containing n repeatingmonomer units: P_(n)=(1−α)(α)^(((n−1)/2))(1−α), for n=odd.

[0220] For a given polymer chain, the number of blocks of length npresent will be given by N_(n)=P_(n)(P_(d)), where P_(d) is the degreeof polymerization-the number of monomers in that chain given by thenumber average molecular weight/monomer molecular weight=M_(n)/42 forpolypropylene.¹ In the table below, the calculated values for N_(n) isgiven as a function of M_(n) and α. For example, a polymer chain ofM_(n)=100,000 and a=0.50 is expected to have 4.65 isotactic blockscontaining 15 monomer units. This is a statistical average and theactual number of isotactic blocks containing 15 monomer units will be anintegral value near 4.65.

[0221] Similarly, this polymer chain is expected to have 0.0045isotactic blocks containing 35 monomer units. While most chains will notcontain an isotactic block of this length, statistically, one out ofevery 222 (=1/0.0045) chains will.

[0222] Although the probability of finding an isotactic block of exactly21 monomer units in a given chain is less than unity, the probability offinding one greater than or equal to 21 monomer units is 1.16, the sumof the N_(n) values for n=21 through n=99. (An exhaustive calculationwould compute up to n=P_(d).) This suggests that there will be,statistically, at least one isotactic block having 21 or more monomerunits in a chain for which M_(n)=100,000 and α=0.50. M_(n) = 100,000200,000 100,000 200,000 100,000 200,000 a = 0.50 0.50 0.62 0.62 0.750.75 n N_(n) N_(n) N_(n) N_(n) N_(n) N_(n)  1 595.2381 1190.4762343.8095 687.6190 148.8095 297.6190  3 297.6190 595.2381 213.1619426.3238 111.6071 223.2143  5 148.8095 297.6190 132.1604 264.320883.7054 167.4107  7 74.4048 148.8095 81.9394 163.8789 62.7790 125.5580 9 37.2024 74.4048 50.8025 101.6049 47.0843 94.1685 11 18.6012 37.202431.4975 62.9950 35.3132 70.6264 13 9.3006 18.6012 19.5285 39.056926.4849 52.9698 15 4.6503 9.3006 12.1076 24.2153 19.8637 39.7273 172.3251 4.6503 7.5067 15.0135 14.8978 29.7955 19 1.1626 2.3251 4.65429.3084 11.1733 22.3466 21 0.5813 1.1626 2.8856 5.7712 8.3800 16.7600 230.2906 0.5813 1.7891 3.5781 6.2850 12.5700 25 0.1453 0.2906 1.10922.2184 4.7137 9.4275 27 0.0727 0.1453 0.6877 1.3754 3.5353 7.0706 290.0363 0.0727 0.4264 0.8528 2.6515 5.3030 31 0.0182 0.0363 0.2644 0.52871.9886 3.9772 33 0.0091 0.0182 0.1639 0.3278 1.4915 2.9829 35 0.00450.0091 0.1016 0.2032 1.1186 2.2372 37 0.0023 0.0045 0.0630 0.1260 0.83891.6779 39 0.0011 0.0023 0.0391 0.0781 0.6292 1.2584 41 0.0006 0.00110.0242 0.0484 0.4719 0.9438 43 0.0003 0.0006 0.0150 0.0300 0.3539 0.707945 0.0001 0.0003 0.0093 0.0186 0.2654 0.5309 47 0.0001 0.0001 0.00580.0115 0.1991 0.3982 49 0.0000 0.0001 0.0036 0.0072 0.1493 0.2986 510.0000 0.0000 0.0022 0.0044 0.1120 0.2240 53 0.0000 0.0000 0.0014 0.00280.0840 0.1680 55 0.0000 0.0000 0.0009 0.0017 0.0630 0.1260 57 0.00000.0000 0.0005 0.0011 0.0472 0.0945 59 0.0000 0.0000 0.0003 0.0007 0.03540.0709 61 0.0000 0.0000 0.0002 0.0004 0.0266 0.0531 63 0.0000 0.00000.0001 0.0003 0.0199 0.0399 65 0.0000 0.0000 0.0001 0.0002 0.0149 0.029967 0.0000 0.0000 0.0000 0.0001 0.0112 0.0224 69 0.0000 0.0000 0.00000.0001 0.0084 0.0168 71 0.0000 0.0000 0.0000 0.0000 0.0063 0.0126 730.0000 0.0000 0.0000 0.0000 0.0047 0.0095 75 0.0000 0.0000 0.0000 0.00000.0035 0.0071 77 0.0000 0.0000 0.0000 0.0000 0.0027 0.0053 79 0.00000.0000 0.0000 0.0000 0.0020 0.0040 81 0.0000 0.0000 0.0000 0.0000 0.00150.0030 83 0.0000 0.0000 0.0000 0.0000 0.0011 0.0022 85 0.0000 0.00000.0000 0.0000 0.0008 0.0017 87 0.0000 0.0000 0.0000 0.0000 0.0006 0.001389 0.0000 0.0000 0.0000 0.0000 0.0005 0.0009 91 0.0000 0.0000 0.00000.0000 0.0004 0.0007 93 0.0000 0.0000 0.0000 0.0000 0.0003 0.0005 950.0000 0.0000 0.0000 0.0000 0.0002 0.0004 97 0.0000 0.0000 0.0000 0.00000.0001 0.0003 99 0.0000 0.0000 0.0000 0.0000 0.0001 0.0002 Sum N_(n) for1.16 2.33 7.59 15.19 33.52 67.04 n = 21

Example 51

[0223] Extimated Block Length of Elastomeric Polymers

[0224] A “block index range” for our polymers might be considered asfollows: For a polymer with m dyad content (alpha) of 0.62, and amolecular weight (Mn) of 100,000 statistics would predict the presenceof at least: one isotactic block of length 25, one block of length 23,two blocks of length 21, four blocks of length 19, seven blocks oflength 17, and so forth. The total numer of blocks having length 21 orgreater (a reasonable cutoff for participation in crystallites) is 7.59,on a statistical basis. The most probable scenario for this polymer isthat it contains seven blocks of sufficient length to participate in acrystalline region.

[0225] For the methyl substituted catalyst (m dyad near 50%), one wouldexpect only 1 block of length 21 or greater for the same molecularweight (not enough: amorphous). For the 3,3,5,5-tetramethylcyclohexylsubstituted catalyst (m dyad near 75%), one would expect 33 blocks oflength 21 or greater for the same molecular weight (too many: a single,crystalline phase)

[0226] Note that our polymers, based on a hemiisotactic regime, arenotpredicted to have isotactic blocks of even length. This is in starkcontrast to the Waymouth elastomers for which a smooth continuum of oddand even length blocks are predicted.

Example 52

[0227] Catalysts for Syndiotactic Polymerization

Example 53

[0228] Syndiotactic Polymerizations TABLE 5 MAO-cocatalyzedpolymerization results with 8, 9, 10, 11, 12, 13, 14, 15, 16, and 17.Metallocene MAO T_(p) Tol. C₃H₆ Time Yield Activity T_(m) ^(a) [r] Entry(mg) (equiv) (° C.) (mL) (mL) (min.) (g) gP/(gmet h) (° C.) (%) M_(w)M_(w)/M_(n)  1  8 (0.5) 2000 0 1.0 30 10 0.48 5700 153 >99 961,000 2.12 2  8 (0.5) 2000 20 1.0 30 10 1.16 14000 148 >98 843,000 1.75  3  8(2.0) 1000 0 2.0 30 10 0.82 2500 149  4  8 (2.0) 1000 20 2.0 30 10 1.444300 146  5  8 (2.0) 1000 0 30.0 3 20 1.44 2200 146 >98  6  8 (2.0) 100020 30.0 3 5 1.68 10000 140  7  9 (3.0) 1000 0 2.0 30 15 0.25 330 11188.6  8  9 (3.0) 1000 20 2.0 30 10 0.98 2000 88 89.8  9 10 (2.0) 1000 02.0 30 10 0.27 800 140 >98 10 10 (2.0) 1000 20 2.0 30 5 1.60 9600 137 1111 (3.0) 1000 0 2.0 30 60 0.27 90 141 92.2 12 11 (3.0) 1000 20 2.0 30 201.27 1300 120 89.7 13 12 (0.5) 2000 0 1.0 30 10 0.26 3100 151 >98 14 12(0.5) 2000 20 1.0 30 10 0.26 3100 147  15^(b) 12 (2.0) 1000 0 2.0 30 101.16 3500 154 97.5 535,000 2.00 16 12 (2.0) 1000 20 2.0 30 10 4.79 14000153 310,000 2.03 17 13 (1.0) 1000 0 2.0 30 10 0.31 1900 142 18 13 (1.0)1000 20 2.0 30 10 1.13 6800 136 19 14 (3.0) 1000 0 2.0 30 30 0.16 110124 20 14 (3.0) 1000 20 2.0 30 15 0.70 940 119 21 15 (2.0) 1000 0 2.0 305 1.12 6700 144 22 15 (2.0) 1000 20 2.0 30 3 2.24 22000 139 23 16 (0.5)2000 0 1.0 30 5 3.00 72000 n.o. 50.2 24 16 (0.5) 2000 20 1.0 30 5 5.09120000 n.o. 50.5 25 17 (0.5) 2000 0 1.0 30 5 1.09 26000 n.o. 81.3 26 17(0.5) 2000 20 1.0 30 5 2.85 68000 n.o. 74.1

Example 54

[0229] Catalysts for Isotactic Polymerization

Example 55

[0230] Isotactic Polymerizations TABLE 6 MAO-cocatalyzed polymerizationresults with 3, 7, 12, 13, 14, 15, 16, 17, and 18. Activity MetalloceneMAO T_(p) Tol. C₃H₆ Time Yield gP T_(m) ^(a) m⁴ Entry (mg) (eq.) (° C.)(mL) (mL) (min.) (g) {overscore ((gmet h))} (° C.) (%) M_(w) M_(w)/M_(n)1 12 (0.5) 2000 0 1.0 30 30 1.50 6000 n.o. 28.4 134,000 3.15 2 12 (0.5)2000 20 1.0 30 10 1.08 13000 n.o. 31.4 81,900 4.38 3 13 (1.0) 1000 0 2.030 15 0.18 730 109 60.2 360,000 1.75 4 13 (1.0) 1000 20 2.0 30 15 1.626500 110 57.5 322,000 1.70 5 14 (2.0) 1000 0 2.0 30 5 0.16 970 129 78.676,700 1.81 6 14 (2.0) 1000 20 2.0 30 30 0.36 360 131 80.0 80,900 2.63 7 7 (2.0) 1000 0 2.0 30 20 0.32 480 137 86.1 8  7 (2.0) 1000 20 2.0 30 200.47 710 138 81.2 9  3 (2.0) 1000 0 2.0 30 20 0.93 1400 126 79.5 10  3(2.0) 1000 20 2.0 30 3 1.01 10000 125 81.5 11 15 (1.0) 1000 0 1.0 30 150.28 1100 144 12 15 (1.0) 1000 20 1.0 30 3 0.66 13000 139 13 16 (1.0)1000 0 2.0 30 10 0.41 158 158 >98 171,00 1.93 14 16 (1.0) 1000 20 2.0 3010 0.83 5000 154 >98 113,000 1.93 15 16 (2.0) 1000 0 2.0 55 60 3.88 1900160 >98 157,000 2.48 16 16 (2.0) 1000 20 2.0 55 10 2.13 6400 156 124,0001.90 17 16 (2.0) 1000 0 2.0 55 10 1.38 4100 159 160,000 1.91 18 16 (2.0)1000 0 30.0 3 180 0.87 140 158 102,000 1.82 19 16 (2.0) 1000 20 30.0 390 0.50 170 148 54,400 2.08 20 17 (3.0) 1000 0 2.0 30 120 0.03 4 n.o. 2117 (3.0) 1000 20 2.0 30 120 0.02 3 n.o. 22 18 (2.0) 1000 0 2.0 30 200.29 440 167 >99 370,000 1.39 23 18 (2.0) 1000 20 2.0 30 20 0.70 1100163 >99 425,000 1.77

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What is claimed is:
 1. A method for producing a polyolefin comprisingcontacting at least one olefin monomer with a metallocene catalyst inthe presence of an activator thereof under suitable reaction conditionsfor a time sufficient to catalytically polymerize said at least oneolefin monomer to form a polymer, wherein said metallocene catalyst hasthe formula

wherein: a) M is selected from the group consisting of a group IIITransition metal, a group IV Transition metal, a group V Transitionmetal, a Lanthamide and an Actinide; b) X is selected from the groupconsisting of fluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀alkyl, C₆ to C₂₀ aryl, alkylaryl, arylalkyl, C₁ to C₁₀ fluoroalkyl, C₆to C₂₀ fluoroaryl, and —OR¹⁷ where R¹⁷ is a C₁ to C₁₀ alkyl or C₆ to C₂₀aryl; and n is the formal oxidation state of M minus 2; c) E¹ isselected from hydrogen, carbon, silicon, and germanium, wherein R¹, R²,and R³ are not present when E¹ is hydrogen; d) E² is selected fromcarbon, silicon, and germanium; e) R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹³, R¹⁴, R¹⁵, and R¹⁶are independently selected from thegroup consisting of hydrogen, C₁ to C₁₀ alkyl, 3 to 10 memberedoptionally substituted cycloalkyl, C₆ to C₁₆ aryl, C₆ to C₁₆ arylalkyl,and Si(R¹⁸)₃ where R¹⁸ is selected from C₁ to C₁₀ alkyl, C₆ to C₁₆ aryland C₃ to C₁₀ cycloalkyl, and wherein two or three of R¹, R² and R³taken together with E¹ can form an optionally substituted 4 to 16 membercyclic group; and f) R⁹ and R¹² are independently selected from thegroup consisting of C₁ to C₁₀ alkyl, 3 to 10 membered optionallysubstituted cycloalkyl, C₆ to C₁₆ aryl, C₆ to C₁₆ arylalkyl, andSi(R¹⁸)₃ where R¹⁸ is selected from a C₁ to C₁₀ alkyl, C₆ to C₁₆ aryland C₃ to C₁₀ cycloalkyl, and wherein any two adjacent members of R⁸,R⁹, R¹² and R¹³, taken together with the atoms to which they areattached, can form an optionally substituted 4 to 16 member cyclicgroup.
 2. The method of claim 1, wherein said reaction conditionscomprise polymerizing the at least one olefin monomer homogeneously insolution.
 3. The method of claim 2, further comprising a solvent in thesolution.
 4. The method of claim 1, wherein said reaction conditionscomprise polymerizing the at least one olefin monomer supported with thecatalyst in a solution.
 5. The method of claim 1, wherein said reactionconditions comprise polymerizing the at least one olefin monomer in thegas phase.
 6. The method of claim 1, wherein said reaction conditionscomprise polymerizing the at least one olefin monomer at high pressure.7. The method of claim 1, wherein said reaction conditions comprisepolymerizing the at least one olefin monomer in bulk monomer.
 8. Themethod of claim 1, wherein said reaction conditions comprisepolymerizing the at least one olefin monomer in a condensed phase of alower molecular weight alk-1-ene.
 9. The method of claim 1, wherein theactivator is selected from an alkylaluminum, a haloalkylaluminum, analkylaluminoxane, aluminoxane, methylaluminoxane, modifiedmethylaluminoxane, a Lewis acid, or a protic acid containing anon-coordinating counter ion.
 10. The method of claim 1, wherein theactivator is B(C₆F₅)₃ or [PhNMe₂H]⁺B(C₆ F₅)⁻ ₄.
 11. The method of claim9, wherein said activator is a Lewis acid or a protic acid and saidcontacting further takes place in the presence of an alkylaluminumcompound.
 12. The method of claim 1, wherein a mixture of olefinmonomers are contacted with a metallocene catalyst to form a copolymeror terpolymer.
 13. The method of claim 1, wherein the monomer isselected from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, and combinations thereof.
 14. The methodof claim 1, wherein a combination of at least two metallocene catalystsis used to contact the monomer.
 15. The method of claim 1 wherein saidcompound has Cs symmetry.
 16. The method of claim 1 wherein R⁹ and R¹²are independently selected from the group consisting of C₃ to C₁₀ alkyl,3 to 10 membered optionally substituted cycloalkyl, C₆ to C₁₆ aryl, C₆to C₁₆ arylalkyl, and Si(R¹⁸)₃ where R¹⁸ is selected from C₁ to C₁₀alkyl, C₆ to C₁₆ aryl and C₃ to C₁₀cycloalkyl, and wherein any twoadjacent members of R⁸, R⁹, R¹² and R¹³, taken together with the atomsto which they are attached, can form an optionally substituted 4 to 16member cyclic group.
 17. The method of claim 1 wherein R¹⁵ and R¹⁶ areeach independently selected from methyl and phenyl.
 18. The method ofclaim 1 wherein R⁸ and R⁹ taken together with the atoms to which theyare attached form an optionally substituted 4 to 16 member cyclic group.19. The method of claim 1 wherein R¹² and R¹³ taken together with theatoms to which they are attached form an optionally substituted 4 to 16member cyclic group.
 20. The method of claim 1 wherein R⁸ and R⁹ and R¹²and R¹³ each pair taken together with the atoms to which they areattached form an optionally substituted 4 to 16 member cyclic group. 21.The method of claim 20 wherein said compound has the formula:


22. The method of claim 21 wherein E¹ and R⁶ are hydrogen and R¹, R² andR³ are absent.
 23. The method of claim 21 wherein E² is carbon.
 24. Themethod of claim 21 wherein R¹⁵ and R¹⁶ are each independently methyl orphenyl.
 25. The method of claim 24 wherein R¹⁵ and R¹⁶ are methyl. 26.The method of claim 24 wherein R¹⁵ and R¹⁶ are phenyl.
 27. The method ofclaim 21 wherein R⁷, R¹⁰, R¹¹ and R¹⁴ are hydrogen.
 28. The method ofclaim 1, wherein E¹ is carbon, silicon or germanium, and wherein two orthree of R¹, R² and R³ taken together with E¹ form an optionallysubstituted 4 to 16 member cyclic group.
 29. The method of claim 1,wherein: M is Ti, Hf or Zr; X is hydride, halogen, alkoxide or C₁-C₇hydrocarbyl; R⁸ and R⁹ and R¹² and R¹³ each pair taken together with theatoms to which they are attached form an optionally substituted 4 to 16member cyclic group; R¹⁵ and R¹⁶ are each independently selected frommethyl and phenyl: E¹ and R⁶ are hydrogen; the activator is chosen froman alkylaluminum, a haloalkylaluminum, an alkylaluminoxane, aluminoxane,methylaluminoxane, modified methylaluminoxane, a Lewis acid, or a proticacid containing a non-coordinating counter ion; and the monomer ischosen from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, and combinations thereof.
 30. The methodof claim 1, wherein: M is Ti, Hf or Zr; X is hydride, halogen, alkoxideor C₁-C₇ hydrocarbyl; R¹⁵ and R¹⁶ are each independently selected frommethyl and phenyl: E¹ is carbon, silicon or germanium, and wherein twoor three of R¹, R² and R³ taken together with E¹ form an optionallysubstituted 4 to 16 member cyclic group; the activator is chosen from analkylaluminum, a haloalkylaluminum, an alkylaluminoxane, aluminoxane,methylaluminoxane, modified methylaluminoxane, a Lewis acid, or a proticacid containing a non-coordinating counter ion; and the monomer ischosen from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, and combinations thereof.
 31. A method forproducing a polyolefin comprising contacting at least one olefin monomerwith a metallocene catalyst in the presence of an activator thereofunder suitable reaction conditions for a time sufficient tocatalytically polymerize said at least one olefin monomer to form apolymer, wherein said metallocene catalyst has the formula

wherein: a) M is selected from the group consisting of a group IIITransition metal, a group IV Transition metal, a group V Transitionmetal, a Lanthamide and an Actinide; b) X is selected from the groupconsisting of fluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀alkyl, C₆ to C₂₀ aryl, alkylaryl, arylalkyl, C₁ to C₁₀ fluoroalkyl, C₆to C₂₀ fluoroaryl, and —OR¹⁷ where R¹⁷ is a C₁ to C₁₀ alkyl or C₆ to C₂₀aryl; and n is the formal oxidation state of M minus 2; c) E¹ isselected from carbon, silicon, and germanium; d) E² is selected fromcarbon, silicon, and germanium; e) R¹, R², R³ are independently selectedfrom the group consisting of hydrogen, C₁ to C₁₀ alkyl, 3 to 10 memberedcycloalkyl optionally substituted with from 1 to 10 C₁ to C₁₀ alkyls, C₆to C₁₆ aryl, C₆ to C₁₆ arylalkyl, and Si(R¹⁸)₃ where R¹⁸ is selectedfrom a C₁ to C₁₀ alkyl, C₆ to C₁₆ aryl and C₃ to C₁₀ cycloalkyl, andwherein two or three of R¹, R² and R³ taken together with E¹ form anoptionally substituted 4 to 16 member cyclic group; and f) R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ are independentlyselected from the group consisting of hydrogen, C₁ to C₁₀ alkyl, 3 to 10membered optionally substituted cycloalkyl, C₆ to C₁₆ aryl, C₆ to C₁₆arylalkyl, and Si(R¹⁸)₃ where R¹⁸ is selected from C₁ to C₁₀ alkyl, C₆to C₁₆ aryl and C₃ to C₁₀ cycloalkyl, and wherein any two adjacentmembers of, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴, takentogether with the atoms to which they are attached, can form anoptionally substituted 4 to 16 member cyclic group, and wherein R¹⁵ andR¹⁶ taken together with E² can form an optionally substituted 4 to 16member cyclic group.
 32. The method of claim 31, wherein said reactionconditions comprise polymerizing the at least one olefin monomerhomogeneously in solution.
 33. The method of claim 32, furthercomprising a solvent in the solution.
 34. The method of claim 31,wherein said reaction conditions comprise polymerizing the at least oneolefin monomer with the catalyst supported in a solution.
 35. The methodof claim 31, wherein said reaction conditions comprise polymerizing theat least one olefin monomer in the gas phase.
 36. The method of claim31, wherein said reaction conditions comprise polymerizing the at leastone olefin monomer at high pressure.
 37. The method of claim 31, whereinsaid reaction conditions comprise polymerizing the at least one olefinmonomer in bulk monomer.
 38. The method of claim 31, wherein saidreaction conditions comprise polymerizing the at least one olefinmonomer in a condensed phase of a lower molecular weight alk-1-ene. 39.The method of claim 31, wherein the activator is selected from analkylaluminum, a haloalkylaluminum, an alkylaluminoxane, aluminoxane,methylaluminoxane, modified methylaluminoxane, a Lewis acid,-or a proticacid containing a non-coordinating counter ion.
 40. The method of claim31, wherein the activator is B(C₆ F₅)₃ or [PhNMe₂H]⁺B(C₆ F₅)⁻ ₄.
 41. Themethod of claim 39, wherein said activator is a Lewis acid or a proticacid and said contacting further takes place in the presence of analkylaluminum compound.
 42. The method of claim 31, wherein a mixture ofolefin monomers are contacted with the metallocene catalyst to form acopolymer or terpolymer.
 43. The method of claim 31, wherein the monomeris selected from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, and combinations thereof.
 44. The methodof claim 31, wherein a combination of at least two metallocene catalystsis used to contact the monomer.
 45. The method of claim 31 wherein saidcompound has C₁ symmetry.
 46. The method of claim 31 wherein R¹, R² andR³ are not hydrogen.
 47. The method of claim 31 wherein two or three ofR¹, R² and R³ form part of a C₆ cyclic group or a substituted C₆ cyclicgroup.
 48. The method of claim 47 wherein said C₆ cyclic group orsubstituted C₆ cyclic group is optionally substituted cyclohexyl,optionally substituted norbornyl, optionally substituted adamantyl, oroptionally substituted 2-methyl-adamantyl.
 49. The method of claim 48wherein R¹⁵ and R16are each independently methyl or phenyl.
 50. Themethod of claim 31, wherein: M is Ti, Hf or Zr; X is hydride, halogen,alkoxide or C₁-C₇ hydrocarbyl; two or three of R¹, R² and R³ form partof a C₆ cyclic group or a substituted C₆ cyclic group C₆ selected fromoptionally substituted cyclohexyl, optionally substituted norbornyl,optionally substituted adamantyl, or optionally substituted2-methyl-adamantyl; R¹⁵ and R¹⁶ are each independently methyl or phenyl;the activator is chosen from an alkylaluminum, a haloalkylaluminum, analkylaluminoxane, aluminoxane, methylaluminoxane, modifiedmethylaluminoxane, a Lewis acid, or a protic acid containing anon-coordinating counter ion; and the monomer is chosen from ethylene,propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, andcombinations thereof.
 51. A method for producing a polyolefin comprisingcontacting at least one olefin monomer with a metallocene catalyst inthe presence of an activator thereof under suitable reaction conditionsfor a time sufficient to catalytically polymerize said at least oneolefin monomer to form a polymer, wherein said metallocene catalyst hasthe formula

wherein: a) M is selected from the group consisting of a group IIITransition metal, a group IV Transition metal, a group V Transitionmetal, a Lanthamide and an Actinide; b) X is selected from the groupconsisting of fluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀alkyl, C₆ to C₂₀ aryl, alkylaryl, arylalkyl, C₁ to C₁₀ fluoroalkyl, C₆to C₂₀ fluoroaryl, and —OR¹⁷ where R¹⁷ is a C₁ to C₁₀ alkyl or C₆ to C₂₀aryl; and n is the formal oxidation state of M minus 2; c) E¹ isselected from carbon, silicon, and germanium; d) E² is selected fromcarbon, silicon, and germanium; e) R¹, R², R³ are independently selectedfrom the group consisting of hydrogen, C₁ to C₁₀ alkyl, 3 to 10 memberedcycloalkyl optionally substituted with from 1 to 10 C₁ to C₁₀ alkyls, C₆to C₁₆ aryl, C₆ to C₁₆ arylalkyl, and Si(R¹⁸)₃ where R¹⁸ is selectedfrom a C₁ to C₁₀ alkyl, C₆ to C₁₆ aryl and C₃ to C₁₀ cycloalkyl, andwherein two or three of R¹, R² and R³ taken together with E¹ can form anoptionally substituted 4 to 16 member cyclic group; and f) R⁴, R⁵, R⁶,R⁷, R¹⁰, R¹¹, R¹⁴, R¹⁵, and R¹⁶ are independently selected from thegroup consisting of hydrogen, C₁ to C₁₀ alkyl, 3 to 10 memberedoptionally substituted cycloalkyl, C₆ to C₁₆ aryl, C₆ to C₁₆ arylalkyl,and Si(R¹⁸)₃ where R¹⁸ is selected from C₁ to C₁₀ alkyl, C₆ to C₁₆ aryland C₃ to C₁₀ cycloalkyl; and g) R⁸, R⁹, R¹² and R¹³ are independentlyselected from the group consisting of C₁ to C₁₀ alkyl, 3 to 10 memberedoptionally substituted cycloalkyl, C₆ to C₁₆ aryl, C₆ to C₁₆ arylalkyl,and Si(R¹⁸)₃ where R¹⁸ is selected from C₁ to C₁₀ alkyl, C₆ to C₁₆ aryland C₃ to C₁₀ cycloalkyl; h) wherein any two adjacent members of R⁵, R⁶,R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and R¹⁴, taken together with the atomsto which they are attached, can form an optionally substituted 4 to 16member cyclic group, and wherein R¹⁵ and R¹⁶ taken together with E² canform an optionally substituted 4 to 16 member cyclic group.
 52. Themethod of claim 51, wherein said reaction conditions comprisepolymerizing the at least one olefin monomer homogeneously in solution.53. The method of claim 52, further comprising a solvent in thesolution.
 54. The method of claim 51, wherein said reaction conditionscomprise polymerizing the at least one olefin monomer with the catalystsupported in a solution.
 55. The method of claim 51, wherein saidreaction conditions comprise polymerizing the at least one olefinmonomer in the gas phase.
 56. The method of claim 51, wherein saidreaction conditions comprise polymerizing the at least one olefinmonomer at high pressure.
 57. The method of claim 51, wherein saidreaction conditions comprise polymerizing the at least one olefinmonomer in bulk monomer.
 58. The method of claim 51, wherein saidreaction conditions comprise polymerizing the at least one olefinmonomer in a condensed phase of a lower molecular weight alk-1-ene. 59.The method of claim 51, wherein the activator is selected from analkylaluminum, a haloalkylaluminum, an alkylaluminoxane, aluminoxane,methylaluminoxane, modified methylaluminoxane, a Lewis acid, or a proticacid containing a non-coordinating counter ion.
 60. The method of claim51, wherein the activator is B(C₆F₅)₃ or [PhNMe₂H]⁺B(C₆F₅)⁻ ₄.
 61. Themethod of claim 59, wherein said activator is a Lewis acid or a proticacid and said contacting further takes place in the presence of analkylaluminum compound.
 62. The method of claim 51, wherein a mixture ofolefin monomers are contacted with the metallocene catalyst to form acopolymer or terpolymer.
 63. The method of claim 51, wherein the monomeris selected from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, and combinations thereof.
 64. The methodof claim 51, wherein a combination of at least two metallocene catalystsis used to contact the monomer.
 65. The method of claim 51, wherein R⁸and R⁹ taken together with the atoms to which they are attached form anoptionally substituted 4 to 16 member cyclic group, and wherein R¹² andR¹³ taken together with the atoms to which they are attached form anoptionally substituted 4 to 16 member cyclic group.
 66. The method ofclaim 65 wherein the metallocene catalyst has the formula


67. The method of claim 51, wherein: M is Ti, Hf or Zr; X is hydride,halogen, alkoxide or C₁-C₇ hydrocarbyl; R⁸ and R⁹ taken together withthe atoms to which they are attached form an optionally substituted 4 to16 member cyclic group, and wherein R¹² and R¹³ taken together with theatoms to which they are attached form an optionally substituted 4 to 16member cyclic group the activator is chosen from an alkylaluminum, ahaloalkylaluminum, an alkylaluminoxane, aluminoxane, methylaluminoxane,modified methylaluminoxane, a Lewis acid, or a protic acid containing anon-coordinating counter ion; and the monomer is chosen from ethylene,propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, andcombinations thereof.
 68. A method for producing a polyolefin comprisingcontacting at least one olefin monomer with a metallocene catalyst inthe presence of an activator thereof under suitable reaction conditionsfor a time sufficient to catalytically polymerize said at least oneolefin monomer to form a polymer, wherein said metallocene catalyst hasthe formula

wherein: a) M is selected from the group consisting of a group IIITransition metal, a group IV Transition metal, a group V Transitionmetal, a Lanthamide and an Actinide; b) X is selected from the groupconsisting of fluorine, chlorine, bromine, iodine, hydrogen, C₁ to C₁₀alkyl, C₆ to C₂₀ aryl, alkylaryl, arylalkyl, C₁ to C₁₀ fluoroalkyl, C₆to C₂₀ fluoroaryl, and -OR¹⁷ where R¹⁷ is a C₁ to C₁₀ alkyl or C₆ to C₂₀aryl; and n is the formal oxidation state of M minus 2; c) E¹ isselected from hydrogen, carbon, silicon, and germanium, wherein R¹, R²,and R³ are not present when E¹ is hydrogen; d) E² is selected fromcarbon, silicon, and germanium; e) R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶are independently selected from thegroup consisting of hydrogen, C₁ to C₁₀ alkyl, 3 to 10 memberedoptionally substituted cycloalkyl, C₆ to C₁₆ aryl, C₆ to C₁₆ arylalkyl,and Si(R¹⁸)₃ where R¹⁸ is selected from C₁ to C₁₀ alkyl, C₆ to C₁₆ aryland C₃ to C₁₀ cycloalkyl, wherein two or three of R¹, R² and R³ takentogether with E¹ can form an optionally substituted 4 to 16 membercyclic group, and wherein any two adjacent members of R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, and R¹⁴, or R¹⁵ and R¹⁶, taken together with the atoms towhich they are attached can form an optionally substituted 4 to 16member cyclic group; and f) R⁶ is selected from the group consisting ofC₁ to C₁₀ alkyl, 3 to 10 membered optionally substituted cycloalkyl, C₆to C₁₆ aryl, C₆ to C₁₆ arylalkyl, and Si(R¹⁸)₃ where R¹⁸ is selectedfrom C to C₁₀alkyl, C₆ to C₁₆ aryl and C₃ to C₁₀ cycloalkyl.
 69. Themethod of claim 68, wherein said reaction conditions comprisepolymerizing the at least one monomer homogeneously in solution.
 70. Themethod of claim 68, wherein said reaction conditions comprisepolymerizing the at least one olefin monomer with the catalyst supportedin a solution.
 71. The method of claim 68, wherein said reactionconditions comprise polymerizing the at least one olefin monomer in thegas phase.
 72. The method of claim 68, wherein said reaction conditionscomprise polymerizing the at least one olefin monomer at high pressure.73. The method of claim 68, wherein said reaction conditions comprisepolymerizing the at least one olefin monomer in bulk monomer.
 74. Themethod of claim 68, wherein said reaction conditions comprisepolymerizing the at least one olefin monomer in a condensed phase of alower molecular weight alk-1-ene.
 75. The method of claim 68, whereinthe activator is selected from an alkylaluminum, a haloalkylaluminum, analkylaluminoxane, aluminoxane, methylaluminoxane, modifiedmethylaluminoxane, a Lewis acid, or a protic acid containing anon-coordinating counter ion.
 76. The method of claim 68, wherein theactivator is B(C₆F₅)₃ or [PhNMe₂H]⁺B(C₆ F₅)⁻ ₄.
 77. The method of claim75, wherein said contacting further takes place in the presence of analkylaluminum compound.
 78. The method of claim 68, wherein a mixture ofolefin monomers are contacted with the metallocene catalyst to form acopolymer or terpolymer.
 79. The method of claim 68, wherein the monomeris selected from ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, and combinations thereof.
 80. The methodof claim 68, wherein a combination of at least two metallocene catalystsis used to contact the monomer.
 81. The method of claim 68, wherein R₆is selected from C¹ to C¹⁰ alkyl and 3 to 10 membered optionallysubstituted cycloalkyl.
 82. The method of claim 68, wherein R⁶ is C₁ toC₁₀ alkyl.
 83. The method of claim 68, wherein R⁶ is methyl.
 84. Themethod of claim 68, further comprising a solvent in the solution. 85.The method of claim 68, wherein: M is Ti, Hf or Zr; X is hydride,halogen, alkoxide or C₁-C₇ hydrocarbyl; R⁶ is C₁ to C₁₀ alkyl; theactivator is chosen from an alkylaluminum, a haloalkylaluminum, analkylaluminoxane, aluminoxane, methylaluminoxane, modifiedmethylaluminoxane, a Lewis acid, or a protic acid containing anon-coordinating counter ion; and the monomer is chosen from ethylene,propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, andcombinations thereof.